Catalyst for synthesizing polyolefins

ABSTRACT

The present invention relates to a method for producing a high-molecular-weight copolymer of polar group-containing allyl monomers comprising monomer units represented by formulae (3) and (4) (in the formulae, R 1  represents a hydrogen atom (H) or hydrocarbon group having 1 to 6 carbon atoms; R 2  represents —OH, —OCOR 3  (R 3  represents hydrocarbon group having 1 to 5 carbon atoms), —N(R 4 ) 2  (R 4  represents a hydrogen atom or hydrocarbon group having 1 to 5 carbon atoms); and n and m are a value representing the molar ratio of each of the monomer units), which has few branches and unsaturated group at the molecular end, by copolymerizing olefin and an allyl compound using a metal complex of group 10 elements in the periodic system represented by formula (I) as a catalyst. 
     The present invention enables providing a high-molecular-weight copolymer of polar group-containing allyl monomers, which copolymer has a novel structure, is available for various applications and has been considered to be difficult to synthesize by other polymerization methods such as radical polymerization; and a method for producing the same.

TECHNICAL FIELD

The present invention relates to a novel organometallic compound; amethod for producing the same; a catalyst for synthesizing polyolefins(a catalyst compound for polymerization of vinyl monomers and forcopolymerization of non-polar olefins and polar olefins); and a methodfor producing a (co)polymer using the catalyst.

BACKGROUND ART

Although polyolefins typified by polyethylene and polypropylene havebeen used versatilely, they are not suitable for all uses. Polyolefinsare inherently non-polar, and therefore inferior in the properties suchas adhesiveness, and persistence, print performance and affinity ofdyes, and limited in their usefulness. However, it is known that suchproperties can be remarkably improved in functionalized polyolefinsobtained by incorporating a small amount of polar functional groups inpolyolefins.

In an effort to expand the application range of polyolefins, methods forincorporating polar functional groups into polyolefins have beenreported (Non-patent documents 1, 2 and the like). Among these methods,the most direct method is to copolymerize olefin monomers withindustrially useful polar vinyl monomers as shown in the followingformula.

Coordination-insertion polymerization (coordination-additionpolymerization) of olefins and polar vinyl monomers using a transitionmetal catalyst was proposed as a useful method for synthesizingfunctionalized polyolefins having a predetermined polymer structure,molecular weight distribution and amount of comonomer to beincorporated. As a late transition metal complex as a catalyst forcoordination-insertion polymerization of olefins and polar vinylmonomers, the most successful one to date is the catalyst in whichα-diimine or phosphine sulfonate ion is coordinated (Patent Document 1,Non-patent Documents 3 and 4). Generally, a highly-linear microstructureof polymer can be obtained by a palladium and nickel catalyst in which aphosphine-sulfonate ion is coordinated. Meanwhile, a palladium andnickel catalyst in which α-diimine is coordinated serves as a catalystfor forming a highly-branched polymer. Among these two importantcatalysts, it has been reported that the catalyst in which aphosphine-sulfonate ion is coordinated exhibits much higher activity inthe copolymerization with polar vinyl monomers such as vinyl acetate,acrylonitrile, vinyl chloride and vinyl ether, compared to the catalystin which α-diimine is coordinated (Non-patent Documents 5, 6 and thelike).

However, a transition metal complex in which phosphine-sulfonate ion iscoordinated has not yet been put to practical use.

Also, a method for copolymerizing ethylene and methyl acrylate using anickel complex having an iminoamide ligand has been proposed (PatentDocument 2), but the method has not yet been put to practical use,either.

PRIOR ART Patent Document

-   Patent Document 1: U.S. Pat. No. 4,689,437-   Patent Document 2: JP-A-2010-265386

Non-Patent Document

-   Non-patent Document 1: Chem. Rev., 2006, 250, 47-   Non-patent Document 2: Prog. Polym. Sci., 1989, 14, 811-   Non-patent Document 3: J. Am. Chem. Soc., 1996, 118, 267-   Non-patent Document 4: Chem. Commun., 2002, 744-   Non-patent Document 5: J. Am. Chem. Soc., 2009, 131, 14606-14607-   Non-patent Document 6: J. Am. Chem. Soc., 2007, 129, 8948

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a catalyst compositionfor polymerizing polyolefins, which composition contains a novelorganometallic compound and has higher activity than a conventionaltransition metal complex in which a phosphine-sulfonate ion iscoordinated.

Method to Solve the Problem

A critical structural feature of a catalyst containingphosphine-sulfonate ester is that there exist one strong σ-donor ligandand one weak σ-donor ligand. To date, a catalyst having high activity incopolymerization of olefins and various polar monomers has been limitedto a phosphine-sulfonate ester type. The present inventors thought thata complex containing a bidentate ligand having an asymmetry structure ofa strong σ-donor ligand and one weak σ-donor ligand other than thecombination of phosphine and sulfonate ester anion can promote formationof a highly-linear random copolymer in the coordination-insertionpolymerization, and have studied various bidentate ligands. As a result,the present inventors have found that a novel cationic palladium complexto which bisphosphine monoxide (BPMO) is coordinated is applicable to acatalyst for polymerization of ethylene and a number of polar vinylmonomers and accomplished the present invention.

That is, the present invention relates to an organometallic compounddescribed in [1] to [21] below, a catalyst composition for(co)polymerization described in [22] to [23] below, a method forproducing copolymers described in [24] to [26] below, and a method forproducing an organometallic compound described in [27] to [28] below.

[1] An organometallic compound containing bisphosphine monoxide (BPMO)represented by formula (I) and a metal center M comprising elementsbelonging to Group 10 in the periodic system forming a complex with BPMO

(in the formula, R^(1a), R^(1b), R^(2a) and R^(2b) may be the same ordifferent with each other, and independently represent a substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 14 carbon atoms, asubstituted or unsubstituted biphenyl group or a substituted orunsubstituted aryl group; a pair of R^(1a) and R^(1b) and a pair ofR^(2a) and R^(2b) may be bonded to form a ring structure; and A¹represents an arylene group, a monocyclic heteroarylene group, bivalentheterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon group, or cycloalkenylene group having 3 to 10 carbonatoms).[2] The organometallic compound as described in [1] above, representedby formula (II)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have the samemeanings as in [1] above; and R³ represents a hydrogen atom, alkyl grouphaving 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atomsor bivalent group represented by A² (A² represents arylene group,monocyclic heteroarylene group, monocyclic cycloalkylene group,monocyclic cycloalkenylene group, monocyclic heterocycloalkylene group,monocyclic heterocycloalkenylene group, heterocyclic group or C2-C4alkylene group); R⁴ represents a neutral electron-donating ligand; R³and R⁴ may be crosslinked; when R³ and R⁴ are crosslinked, L representsa single bond or a bivalent group selected from alkylene group,haloalkylene group, alkenylene group and alkynilene group; and when R³and R⁴ are not crosslinked (that is, when L does not exist), R⁴ needsnot to exist; and X⁻ represents a counterion of the cationicorganometallic compound).[3] The organometallic compound as described in [2] above, whereinligand R⁴ is:(i) selected from pyridine, substituted pyridine, a nitrile compound,ammonia, alkylamine, substituted alkylamine, arylamine and substitutedarylamine; or(ii) represented by formula (1)

(in the formula, W represents C or S; Z is selected from O, S, NH orNR^(a) (R^(a) represents alkyl group or aryl group) and Y needs not toexist; when Y exists, Y is selected from O, S, NH or NR^(b) (R^(b)represents alkyl group or aryl group); R⁵ represents a substituted orunsubstituted alkyl group having 1 to 10 carbon atoms, —OR^(c) (R^(c)represents alkyl group or aryl group) or —NR^(d) ₂ (R^(d) representsalkyl group or aryl group)).[4] The organometallic compound as described in any one of [1] to [3]above represented by formula (III)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), A¹ and X⁻ have thesame meanings as in formula (I) in [1] above and formula (II) in [2]above; R⁶ represents alkyl group having 1 to 10 carbon atoms, alkenylgroup or aryl group; R⁷, R⁸ and R⁹ independently represent alkyl groupor alkoxy group having 1 to 4 carbon atoms).[5] The organometallic compound as described in any one of [1] to [3],represented by formula (IIa)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁶, A¹ and X⁻ havethe same meanings as in [1] to [3] above).[6] The organometallic compound as described in [4] or [5] above,wherein A1 is substituted or unsubstituted phenylene group, substitutedor unsubstituted naphthylene group or substituted or unsubstitutedmethylene group.[7] The organometallic compound as described in any one of [4] to [6]above, wherein R^(1a), R^(1b), R^(2a) and R^(2b) independently representbranched alkyl group having 3 to 6 carbon atoms.[8] The organometallic compound as described in any one of [1] to [7]above, wherein both of R^(1a) and R^(1b) are isopropyl group or t-butylgroup.[9] The organometallic compound as described in any one of [1] to [8]above, wherein both of R^(2a) and R^(2b) are t-butyl group.[10] The organometallic compound as described in any one of [4] to [9]above, wherein X is selected from SbF₆, BPh₄, BArF₄(ArF₄=[3,5-(CF₃)₂C₆H₃]₄), BF₄ and PF₆.[11] The organometallic compound as described in any one of [4] to [10]above, wherein M is palladium.[12] The organometallic compound as described in any one of [1] to [3]above, represented by formula (IV)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, A¹, A², Y, Z, Wand X⁻ have the same meanings as in [1] to [3] above).[13] The organometallic compound as described in [12] above, wherein A1is a substituted or unsubstituted phenylene group, a substituted orunsubstituted naphthylene group or a substituted or unsubstitutedmethylene group.[14] The organometallic compound as described in [12] or [13] above,represented by formula (V)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), A², R⁵ and X⁻ havethe same meanings as in [1] to [3] above; R¹¹ may not exist orrepresents alkyl group having 1 to 10 carbon atoms, 1 to 4 of whichexist on a benzene ring, and the existing two or more R¹¹'s may be thesame or different with each other).[15] The organometallic compound as described in [14] above, wherein A²is substituted or unsubstituted phenylene group or naphthylene group.[16] The organometallic compound as described in [15] above, representedby formula (VI)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, R¹¹ and X⁻ havethe same meanings as in [1] to [3] and [14] above).[17] The organometallic compound as described in any one of [12] to [16]above, wherein R^(1a), R^(1b), R^(2a) and R^(2b) are independentlybranched alkyl group having 3 to 14 carbon atoms.[18] The organometallic compound as described in any one of [12] to [17]above, wherein both of R^(1a) and R^(1b) are isopropyl group.[19] The organometallic compound as described in any one of [12] to [18]above, wherein both of R^(2a) and R^(2b) are t-butyl group.[20] The organometallic compound as described in any one of [12] to [19]above, wherein X⁻ is selected from SbF₆ ⁻, BPh₄ ⁻, BArF₄ ⁻, BF₄ ⁻ andPF₆ ⁻.[21] The organometallic compound as described in any one of [12] to [20]above, wherein M is palladium.[22] A catalyst composition for polymerizing vinyl monomers, whichcontains the organometallic compound described in any one of [1] to [21]above.[23] A catalyst composition for copolymerizing non-polar olefins andpolar olefins, which contains the organometallic compound described inany one of [1] to [21] above.[24] A method for producing copolymers, comprising a process of reactingnon-polar olefins with polar olefins under polymerization conditions inthe presence of the catalyst composition containing the organometalliccompound described in any one of [1] to [21] above.[25] The method for producing copolymers as described in [24] above,wherein polar olefins are represented by formula (VII)

CH₂═CR¹³R¹⁴  (VII)

(in the formula, R¹³ represents a hydrogen atom or methyl group; R¹⁴represents —COOR¹⁵, —CN, —OCOR¹⁵, —OR¹⁵, —CH₂—OCOR¹⁵, —CH₂OH,—CH₂—N(R¹⁶)₂ or —CH₂-Hal (R¹⁵ represents a hydrogen atom, alkyl grouphaving 1 to 5 carbon atoms or aryl group having 6 to 18 carbon atoms;R¹⁶ represents a hydrogen atom, alkyl group having 1 to 5 carbon atoms,aryl group having 6 to 18 carbon atoms or alkoxycarbonyl group; and Halrepresents a halogen atom)).[26] The method for producing copolymers as described in [25] above,wherein R¹⁴ is —CH₂—OCOR¹⁵, —CH₂OH, —CH₂—N(R¹⁶)₂ or —CH₂-Hal (R¹⁵, R¹⁶and Hal have the same meanings as described in [25] above).[27] A method for producing an organometallic compound represented byformula (III)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁶, R⁷, R⁸, R⁹, A¹and X have the meanings as set forth below), comprising:

-   (1) A process of reacting free bisphosphine monoxide (BPMO)    represented by formula (I)

(in the formula, R^(1a), R^(1b), R^(2a) and R^(2b) may be the same ordifferent with each other, and independently represent a substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 14 carbon atoms, asubstituted or unsubstituted biphenyl group or a substituted orunsubstituted aryl group; a pair of R^(1a) and R^(1b) and a pair ofR^(2a) and R^(2b) may be bonded to form a ring structure; and A′represents an arylene group, a monocyclic heteroarylene group,heterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon group, or cycloalkenylene group having 3 to 10 carbonatoms) and (1,5-cyclooctadiene) MR⁶Xa (M represents an element belongingto Group 10 in the periodic system; R⁶ represents alkyl group having 1to 10 carbon atoms, alkenyl group or aryl group; and Xa represents ahalogen atom); and

-   (2) A process of treating the generated (BPMO)(1,5-cyclooctadiene)    MR⁶Xa complex with a metal salt represented by M²X (M² represents a    monovalent metal ion selected from Ag, Li, Na and K; and X    represents a counteranion selected from SbF₆, BPh₄, BArF₄, BF₄ and    PF₆) and a compound represented by formula (2)

(in the formula, R⁷, R⁸ and R⁹ independently represent a hydrogen atom,alkyl group having 1 to 4 carbon atoms or alkoxy group).[28] A method for producing an organometallic compound represented byformula (IVa)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, A¹, A² and Xhave the meanings as set forth below), comprising:

-   (1) A process of reacting free bisphosphine monoxide (BPMO)    represented by formula (I)

(in the formula, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have the meaningsas described in [1] above) with a compound represented by formula (3)

(in the formula, M represents an element belonging to Group 10 in theperiodic system; A² represents an arylene group, a monocyclicheteroarylene group, a monocyclic cycloalkylene group, a monocycliccycloalkenylene group, a monocyclic heterocycloalkylene group, amonocyclic heterocycloalkenylene group, heterocyclic or C2-C4 alkylenegroup; R⁵ represents substituted or unsubstituted alkyl group having 1to 10 carbon atoms, OR^(c) (R^(c) represents alkyl group or aryl group)or NR^(d) ₂ (R^(d) represents alkyl group or aryl group); and Xbrepresents halogen); and

-   (2) a process of adding a metal salt represented by M²X (M²    represents a monovalent metal ion selected from Ag, Li, Na and K;    and X represents a counteranion selected from SbF₆, BPh₄, BArF₄, BF₄    and PF₆) to the reaction product of process (1).

Effects of the Invention

The catalyst composition containing a novel organometallic compound ofthe present invention has a high activity in the coordination-insertionpolymerization of ethylene and polar vinyl monomers. By using thecatalyst composition of the present invention, a highly-linear polymercan be obtained and further, a copolymer in which polar monomers arerandomly distributed in polymer chains can be obtained. Thus, thecatalyst composition containing a novel organometallic compound of thepresent invention is extremely useful since it enables the production ofindustrially-useful functionalized polyolefin.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 ¹³C-NMR chart of the product of Example 5

FIG. 2 ¹³C-NMR chart of the product of Example 10

FIG. 3 ¹³C-NMR chart of the product of Example 12

FIG. 4 ¹³C-NMR chart of the product of Example 14

FIG. 5 ¹³C-NMR chart of the product of Example 16

FIG. 6 ¹³C-NMR chart of the product of Example 18

MODE FOR CARRYING OUT THE INVENTION

The organometallic compound of the present invention is a compoundcomprising a complex formed by bisphosphine monoxide (BPMO) representedby formula (I) as a ligand with metal center M composed of an elementbelonging to Group 10 in the periodic system.

Here, M represents an element belonging to Group 10 in the periodicsystem.

In formula (I), R^(1a), R^(1b), R^(2a), and R^(2b) may be the same ordifferent with each other and independently represent substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, substituted orunsubstituted cycloalkyl group having 3 to 14 carbon atoms, substitutedor unsubstituted biphenyl group (C₆H₅—C₆H₄—) or substituted orunsubstituted aryl group; and preferably substituted or unsubstitutedalkyl group having 1 to 14 carbon atoms.

Also, a pair of R^(1a) and R^(1b) and a pair of R^(2a) and R^(2b) may bebonded and form a ring structure.

Specific examples of the [(R^(1a))(R^(1b))P] and [(R^(2a))(R^(2b))P]sites include the following structures. In the following structureformulae, the bonds between P and O, and P and A¹ are omitted.

A¹ represents an arylene group, a monocyclic heteroarylene group,bivalent heterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon group, or cycloalkenylene group having 3 to 10 carbonatoms. Examples of A¹ include ortho-phenylene group, 1,2-naphthylenegroup, 1,8-naphthylene group, 1,2-cyclohexylene group,1,2-cyclopentylene group, 1,2-vinylene group, 1,2-cyclohexenylene group,1,2-cyclopentenylene group, methylene group, and ethylene group which isunsubstituted or in which alkyl group, alkoxy group, amino group orester group may be substituted. From the viewpoint of the ease ofsynthesis, ortho-phenylene group, 1,2-naphthylene group, 1,8-naphthylenegroup and methylene group are preferable, and ortho-phenylene group andmethylene group are more preferable.

One embodiment of the present invention is an organometallic compoundrepresented by formula (II).

In formula (II), M, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have themeanings as described above.

R³ represents alkyl group having 1 to 10 carbon atoms, alkenyl grouphaving 1 to 10 carbon atoms or bivalent group represented by A²; and A²represents arylene group, monocyclic heteroarylene group, monocycliccycloalkylene group, monocyclic cycloalkenylene group, monocyclicheterocycloalkylene group, monocyclic heterocycloalkenylene group, orheterocyclic or C2-C4 alkylene group.

R⁴ represents a neutral electron-donating ligand. Examples of a neutralelectron-donating ligand include pyridine, substituted pyridine,quinoline, substituted quinoline, nitrile compounds, ammonia,alkylamine, substituted alkylamine, arylamine, substituted arylamine,sulfoxide, alkylphosphine, substituted alkylphosphine, arylphosphine,substituted arylphosphine, alkyl phosphite, substituted alkyl phosphite,aryl phosphite, substituted aryl phosphite, aliphatic ether, substitutedaliphatic ether, cyclic ether, and substituted cyclic ether.Specifically, pyridine, 2,6-dimethylpyridine,4-(N,N-dimethylamino)pyridine (DMAP); quinoline, 2-methylquinoline;trialkylamine having 1 to 10 carbon atoms,N,N,N′,N′-tetramethylethylenediamine (TMEDA); dialkylaminoaniline,2,6-dimethylaniline, 2,6-diisopropylaniline, acetonitrile, benzonitrile;dimethylsulfoxide (DMSO); trimethylphosphine, triisopropylphosphine,tributylphosphine, tri(t-butyl)phosphine, triphenylphosphine,tris(o-tolyl)phosphine, trifurylphosphine; diethyl ether;tetrahydrofuran, 1,4-dioxane; and 1,2-dimethoxyethane.

In another embodiment of the present invention, R⁴ is selected frompyridine, substituted pyridine, nitrile compounds, ammonia, alkylamine,substituted alkylamine, arylamine and substituted arylamine; andpreferably pyridine or substituted pyridine.

In another embodiment of the present invention, ligand R⁴ is representedby formula (1).

In formula (1), W represents a carbon atom (C) or a sulfur atom (S), Zis selected from an oxygen atom (O), S, NH or NR^(a) (R^(a) representsalkyl group or aryl group); Y is selected from O, S, NH or NR^(b) (R^(b)represents alkyl group or aryl group); R⁵ is substituted orunsubstituted alkyl group having 1 to 10 carbon atoms, OR^(c) (R^(c)represents alkyl group or aryl group) or NR^(d) ₂ (R^(d) representsalkyl group or aryl group).

R³ and R⁴ may be crosslinked, and when R³ and R⁴ are crosslinked, Lrepresents a single bond or bivalent group selected from alkylene group,haloalkylene group, alkenylene group and alkynylene group. When R³ andR⁴ are not crosslinked, L does not exist.

R⁴ needs not exist. When R⁴ does not exist, the embodiment of theorganometallic compound represented by formula (II) becomes thethreefold-coordination organometallic compound represented by formula(IIa).

In the formula, M, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have themeanings as described above.

X⁻ represents a counterion of the cationic organometallic complex. Thecounterion represented by X− may be any monovalent anion. Further, ifthe charge number per atom of the metal center (M) is monovalent, X⁻ maybe a polyvalent anion. Specifically, examples include sulfate ion (SO₄²⁻), nitrate ion (NO₃ ⁻), carbonate ion (CO₃ ²⁻), perchlorate ion (ClO₄⁻), halide ion such as chloride ion (Cl⁻), bromide ion (Br⁻) and iodideion (I⁻); borate ion such as tetrafluoroborate (BF₄ ⁻),bromotrifluoroborate (BBrF₃ ⁻), chlorotrifluoroborate (BClF₃ ⁻),trifluoromethoxyborate (BF₃(OCH₃)⁻), trifluoroethoxyborate(BF₃(OC₂H₅)⁻), trifluoroallyloxyborate (BF₃(OC₃H₅)⁻), tetraphenylborate(B(C₆H₅)₄ ⁻), tetrakis(3,5-bis(trifluoromethyl)phenyl)borate(B(3,5-(CF₃)₂C₆H₃)₄ ⁻=BArF₄ ⁻), bromotriphenylborate (BBr(C₆H₅)₃ ⁻),chlorotriphenylborate (BCl(C₆H₅)₃ ⁻), methoxytriphenylborate(B(OCH₃)(C₆H₅)₃ ⁻), ethoxytriphenylborate (B(OC₂H₅)(C₆H₅)₃ ⁻),allyloxytriphenylborate (B(OC₃H₅)(C₆H₅)₃ ⁻),tetrakis(pentafluorophenyl)borate (B(C₆F₅)₄ ⁻),bromotris(pentafluorophenyl)borate (BBr(C₆F₅)₃ ⁻),chlorotris(pentafluorophenyl)borate (BCl(C₆F₅)₃ ⁻),methoxytris(pentafluorophenyl)borate (B(OCH₃)(C₆H₅)₃ ⁻),ethoxytris(pentafluorophenyl)borate (B(OC₂H₅)(C₆F₅)₃ ⁻) andallyloxytris(pentafluorophenyl)borate (B(OC₃H₅)(C₆F₅)₃ ⁻); sulfonate ionsuch as methanesulfonate ion (CH₃SO₃ ⁻), trifluoromethanesulfonate(CF₃SO₃ ⁻), nonafluorobutanesulfonate (C₄F₉SO₃ ⁻), benzenesulfonate(C₆H₅SO₃ ⁻) and p-toluenesulfonate (p-CH₃—C₆H₄SO₃ ⁻); carboxylate ionsuch as acetate ion (CH₃CO₂ ⁻), trifluoroacetate ion (CF₃CO₂ ⁻),trichloroacetate ion (CCl₃CO₂ ⁻), propionate ion (C₂H₅CO₂—) and benzoateion (C₆H₅CO₂ ⁻); phosphate ion such as hexafluorophosphate ion (PF₆ ⁻);arsenate ion such as hexafluoroarsenate ion (AsF₆ ⁻); antimonate ionsuch as hexafluoroantimonate (SbF₆ ⁻); and silicate ion such ashexafluorosilicate (SiF₆ ⁻). Among these counterions, preferred arethose in which X⁻ is SbF₆ ⁻, BPh₄ ⁻, BArF₄ ⁻, BF₄ ⁻ and PF₆ ⁻.

Among the organometallic compounds represented by formula (II) of thepresent invention, a preferred embodiment is an organometallic compoundrepresented by formula (III).

In formula (III), M, R^(1a), R^(1b), R^(2a), R^(2b), A¹ and X⁻ have themeanings as described above.

R⁶ represents an alkyl group, alkenyl group or aryl group, which has 1to 10 carbon atoms.

R⁷, R⁸ and R⁹ independently represent a hydrogen atom, or alkyl group oralkoxy group, which has 1 to 4 carbon atoms.

In formula (III), A¹ is preferably a substituted or unsubstitutedphenylene group, substituted or unsubstituted naphthylene group, orsubstituted or unsubstituted methylene group.

Among the organometallic compounds represented by formula (III) of thepresent invention, a preferred embodiment is an organometallic compoundrepresented by the following formula (IIIa).

Here, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁷, R⁸, R⁹ and X⁻ have themeanings as described above.

R¹⁰ does not exist, or represents an alkyl group having 1 to 10 carbonatoms, which is substituted with an arbitrary replaceable hydrogen in abenzene ring, and when two or more R¹⁰'s exist, they may be the same ordifferent with each other.

Meanwhile, an organometallic compound represented by formula (IIIc) is apreferred embodiment among the organometallic compounds represented byformula (III) as well.

In the formula, R^(1a), R^(1b), R^(2a), R^(2b), R⁷, R⁸, R⁹ and X⁻ havethe meanings as described above.

R^(13a) and R^(13b) independently represent a hydrogen atom, alkyl grouphaving 1 to 10 carbon atoms or aryl group having 6 to 12 carbon atoms,and may be the same or different with each other. R^(13a) and R^(13b)may bond to each other to form a crosslinked structure.

In formulae (III), (IIIa) or (IIIc), R^(1a), R^(1b), R^(2a) and R^(2b),independently from each other, are preferably a substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, and morepreferably, a branched alkyl group having 3 to 5 carbon atoms. In aconventional transition metal complex to which phosphine-sulfonate iscoordinated, an aryl group have been used as a substituent of aphosphorus atom. In a novel organometallic compound of the presentinvention to which bisphosphine monoxide (BPMO) is coordinated, it wasfound that the compound exhibited higher activity in polymerization ofolefins when an alkyl group was used as a substituent of a phosphorusatom than the case where an aryl group was used.

In the present invention, it is especially preferable that R^(1a),R^(1b), R^(2a) and R^(2b) in formula (III) are an isopropyl group ort-butyl group, independently from each other. It is particularlypreferable that R^(1a) and R^(1b) are an isopropyl group and R^(2a) andR^(2b) are a t-butyl group.

In an embodiment where the organometallic compound of the presentinvention is a compound represented by formula (IIIc), both of R13a andR13b in formula (IIIc) are preferably a hydrogen atom or a methyl group,more preferably a hydrogen atom.

In formula (III), M is an element belonging to Group 10 in the periodicsystem, preferably nickel or palladium, and more preferably, palladium.

Among the organometallic compounds represented by formula (II) of thepresent invention, another preferred embodiment is an organometalliccompound represented by formula (IV).

In formula (IV), M, R^(1a), R^(1b), R^(2a), R^(2b), A¹ and X⁻ have themeanings as described above.

In the organometallic compound of formula (IV), the portion representedby formula (1) forms a closed ring structure within a molecule. Here, aconventional transition metal complex to which phosphine-sulfonate iscoordinated was stabilized using strong Lewis base such as pyridine, butit tended to inhibit vinyl monomer from inserting/coordinating to themetal. In the novel organometallic compound represented by formula (IV),introducing weak Lewis base as “Z” can stabilize the complex by forminga closed ring structure within a molecule, as well as facilitate theinsertion/coordination of the vinyl monomer to the metal.

Here, as defined in formula (1), W represents C or S; Z is selected fromO, S, NH or NR^(a) (R^(a) represents alkyl group or aryl group) and whenY exists, Y is selected from O, S, NH or NR^(b) (R^(b) represents alkylgroup or aryl group); R⁵ represents a substituted or unsubstituted alkylgroup having 1 to 10 carbon atoms, OR^(c) (R^(c) represents alkyl groupor aryl group), NR^(d) ₂ or SR^(d) (R^(d) represents alkyl group or arylgroup). When Y does not exist, W is directly bonded to A². Specificexamples of ligands represented by YW(=Z)R⁵ (1) include OC(═O)R,OC(═O)OR, NHC(═O)R, NHC(═O)OR, C(═O)OR, OC(═S)R, OC(═S)SR, C(═O)NHR,C(═O)N(R)₂ and OS(═O)OR(R represents an alkyl or aryl group, and whentwo R's exist, they may be the same or different).

In one preferred embodiment of the present invention, the organometalliccompound is represented by formula (IVa) in which the ligand representedby YW(=Z)R⁵ (1) is NH(C═O)R⁵.

In the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, A¹, A² and X⁻have the same meanings as described above.

A² represents arylene group, monocyclic heteroarylene group, monocycliccycloalkylene group, monocyclic cycloalkenylene group, monocyclicheterocycloalkylene group, monocyclic heterocycloalkenylene group,heterocyclic group or C2-C4 alkylene group. Specifically, examples of A²include o-phenylene group, 1,2-naphthylene group, 1,8-naphthylene group,1,2-cyclohexylene group, 1,2-cyclopentylene group; ethylene group(—CH₂—CH₂—), propylene group (—CH₂—CH₂—CH₂—) and butylene group(—CH₂—CH₂—CH₂—CH₂—) group, which are unsubstituted, or wherein alkylgroup, alkoxy group, amino group, ester group may be substituted.

In formula (IV), A¹ represents arylene group, monocyclic heteroarylenegroup, heterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon atoms, or cycloalkenylene group having 3 to 10 carbonatoms. Preferred are substituted or unsubstituted phenylene group,substituted or unsubstituted naphthylene group, or substituted orunsubstituted methylene group.

Among the organometallic compounds represented by formula (IV) of thepresent invention, one preferred embodiment is an organometalliccompound represented by formula (V).

In formula (V), M, R^(1a), R^(1b), R^(2a), R^(2b), A², R⁵ and X⁻ havethe same meanings as described above.

R¹¹ does not exist, or represents an alkyl group having 1 to 10 carbonatoms, which is substituted with an arbitrary replaceable hydrogen in abenzene ring, and when two or more R¹¹'s exist, they may be the same ordifferent with each other.

In formula (V), A² represents arylene group, monocyclic heteroarylenegroup, monocyclic cycloalkylene group, monocyclic cycloalkenylene group,monocyclic heterocycloalkylene group, monocyclic heterocycloalkenylenegroup, or heterocyclic or C2-C4 alkylene group. Preferred aresubstituted or unsubstituted phenylene group and substituted orunsubstituted naphthylene group.

Among the organometallic compounds represented by formula (IV) of thepresent invention, another preferred embodiment is the organometalliccompound represented by the following formula (VI).

In formula (VI), M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, R¹¹ and X⁻ havethe same meanings as described above.

R¹² does not exist, or represents an alkyl group having 1 to 10 carbonatoms, which is substituted with an arbitrary replaceable hydrogen in abenzene ring, and when two or more R¹²'s exist, they may be the same ordifferent with each other.

In formulae (IV) to (VI), R^(1a), R^(1b), R^(2a) and R^(2b),independently from each other, are preferably substituted orunsubstituted alkyl group having 1 to 10 carbon atoms, more preferably abranched alkyl group having 3 to 5 carbon atoms. It is preferable thatR^(1a), R^(1b), R^(2a) and R^(2b) are an isopropyl group or t-butylgroup, independently from each other. It is particularly preferable thatR^(1a) and R^(1b) are an isopropyl group and R^(2a) and R^(2b) are at-butyl group.

In formulae (IV) to (VI), M is an element belonging to Group 10 in theperiodic system and preferably nickel or palladium, more preferably,palladium.

An example of the organometallic compounds represented by formula (III)of the present invention, wherein A¹ is phenylene, can be synthesized,for example, by the following scheme 1.

The compound can be obtained by, after mixing free bisphosphine monoxide(BPMO) and (cod)PdMeCl (cod=1,5-cyclooctadiene), treating theintermediate (BPMO)(cod)PdMeCl complex with silver hexafluoroantimonateand 2,6-lutidine.

Specific examples of the organometallic compounds represented byformulae (II) to (VI) of the present invention are described below.

Regarding the case where R¹⁰ does not exist in formula (IIIa) (i.e.where there is no substituent of R¹⁰ in a benzene ring), specificexamples of the organometallic compounds represented by the followingformula (IIIb) of the present invention are shown in Table I.

In Table I, H represents a hydrogen atom, Me represents a methyl group,Et represents an ethyl group, n-Pr represents an n-propyl group, i-Prrepresents an isopropyl group, tert-Bu represents a t-butyl group,NeoPen represents a neopentyl group, CyHex represents a cyclohexylgroup, CyPen represents a cyclopentyl group, 1-Ada represents a1-adamantyl group, and Biph represents 2′-[2,6-bis(dimethoxy)]biphenylgroup. HIPT represents a group represented by the following formula.

TABLE I Compound R No. 1a 1b 2a 2b 6 7 8 9 X 1 i-Pr i-Pr i-Pr i-Pr Me HH H SbF₆ 2 i-Pr i-Pr i-Pr i-Pr Me Me Me H SbF₆ 3 i-Pr i-Pr i-Pr i-Pr MeMe Me Me SbF₆ 4 i-Pr i-Pr i-Pr i-Pr Me Me H Me SbF₆ 5 i-Pr tert-Bu i-Pri-Pr Me H H H SbF₆ 6 i-Pr i-Pr tert-Bu i-Pr Me H H H SbF₆ 7 i-Pr tert-Bui-Pr tert-Bu Me H H H SbF₆ 8 i-Pr i-Pr tert-Bu tert-Bu Me H H H SbF₆ 9i-Pr i-Pr tert-Bu tert-Bu Me Me Me H SbF₆ 10 i-Pr i-Pr tert-Bu tert-BuMe Me Me Me SbF₆ 11 i-Pr i-Pr tert-Bu tert-Bu Me Me H Me SbF₆ 12 i-Pri-Pr NeoPen NeoPen Me H H H SbF₆ 13 i-Pr i-Pr NeoPen NeoPen Me Me H MeSbF₆ 14 i-Pr i-Pr NeoPen NeoPen Me Me Me Me SbF₆ 15 i-Pr i-Pr NeoPenNeoPen Me Me H Me SbF₆ 16 i-Pr i-Pr CyHex CyHex Me H H H SbF₆ 17 i-Pri-Pr CyHex CyHex Me Me H Me SbF₆ 18 i-Pr i-Pr CyPen CyPen Me H H H SbF₆19 i-Pr i-Pr CyPen CyPen Me Me H Me SbF₆ 20 i-Pr i-Pr Me Me Me H H HSbF₆ 21 i-Pr i-Pr Me Me Me Me Me H SbF₆ 22 i-Pr i-Pr Me Me Me Me Me MeSbF₆ 23 i-Pr i-Pr Me Me Me Me H Me SbF₆ 24 i-Pr i-Pr Et Et Me H H H SbF₆25 i-Pr i-Pr Et Et Me Me H Me SbF₆ 26 i-Pr i-Pr n-Pr n-Pr Me H H H SbF₆27 i-Pr i-Pr n-Pr n-Pr Me Me H Me SbF₆ 28 tert-Bu tert-Bu i-Pr i-Pr Me HH H SbF₆ 29 tert-Bu tert-Bu i-Pr i-Pr Me Me Me H SbF₆ 30 tert-Bu tert-Bui-Pr i-Pr Me Me Me Me SbF₆ 31 tert-Bu tert-Bu i-Pr i-Pr Me Me H Me SbF₆32 tert-Bu tert-Bu tert-Bu tert-Bu Me H H H SbF₆ 33 tert-Bu tert-Butert-Bu tert-Bu Me Me Me H SbF₆ 34 tert-Bu tert-Bu tert-Bu tert-Bu Me MeMe Me SbF₆ 35 tert-Bu tert-Bu tert-Bu tert-Bu Me Me H Me SbF₆ 36 tert-Butert-Bu tert-Bu i-Pro Me H H H SbF₆ 37 tert-Bu tert-Bu NeoPen NeoPen MeH H H SbF₆ 38 tert-Bu tert-Bu NeoPen NeoPen Me Me H Me SbF₆ 39 tert-Butert-Bu NeoPen NeoPen Me Me Me Me SbF₆ 40 tert-Bu tert-Bu NeoPen NeoPenMe Me H Me SbF₆ 41 tert-Bu tert-Bu CyHex CyHex Me H H H SbF₆ 42 tert-Butert-Bu CyHex CyHex Me Me H Me SbF₆ 43 tert-Bu tert-Bu CyPen CyPen Me HH H SbF₆ 44 tert-Bu tert-Bu CyPen CyPen Me Me H Me SbF₆ 45 tert-Butert-Bu Me Me Me H H H SbF₆ 46 tert-Bu tert-Bu Me Me Me Me H Me SbF₆ 47tert-Bu tert-Bu Et Et Me H H H SbF₆ 48 tert-Bu tert-Bu Et Et Me Me H MeSbF₆ 49 tert-Bu tert-Bu n-Pr n-Pr Me H H H SbF₆ 50 tert-Bu tert-Bu n-Prn-Pr Me Me H Me SbF₆ 51 NeoPen NeoPen i-Pr i-Pr Me H H H SbF₆ 52 NeoPenNeoPen i-Pr i-Pr Me Me H Me SbF₆ 53 NeoPen NeoPen tert-Bu tert-Bu Me H HH SbF₆ 54 NeoPen NeoPen tert-Bu tert-Bu Me Me H Me SbF₆ 55 NeoPen NeoPenNeoPen NeoPen Me H H H SbF₆ 56 NeoPen NeoPen NeoPen NeoPen Me Me H MeSbF₆ 57 NeoPen NeoPen CyHex CyHex Me H H H SbF₆ 58 NeoPen NeoPen Me MeMe Me H Me SbF₆ 59 NeoPen NeoPen Et Et Me Me H Me SbF₆ 60 NeoPen NeoPenn-Pr n-Pr Me Me H Me SbF₆ 61 CyHex CyHex i-Pr i-Pr Me Me H Me SbF₆ 62CyHex CyHex tert-Bu tert-Bu Me Me H Me SbF₆ 63 CyHex CyHex Me Me Me Me HMe SbF₆ 64 CyHex CyHex Et Et Me Me H Me SbF₆ 65 CyHex CyHex n-Pr n-Pr MeMe H Me SbF₆ 66 CyPen CyPen i-Pr i-Pr Me Me H Me SbF₆ 67 CyPen CyPentert-Bu tert-Bu Me Me H Me SbF₆ 68 CyPen CyPen Me Me Me Me H Me SbF₆ 69CyPen CyPen Et Et Me Me H Me SbF₆ 70 Me Me i-Pr i-Pr Me Me H Me SbF₆ 71Me Me tert-Bu tert-Bu Me Me H Me SbF₆ 72 Me Me NeoPen NeoPen Me Me H MeSbF₆ 73 Me Me CyHex CyHex Me Me H Me SbF₆ 74 Me Me Et Et Me Me H Me SbF₆75 Me Me n-Pr n-Pr Me Me H Me SbF₆ 76 Et Et i-Pr i-Pr Me Me H Me SbF₆ 77Et Et tert-Bu tert-Bu Me Me H Me SbF₆ 78 Et Et NeoPen NeoPen Me Me H MeSbF₆ 79 Et Et CyHex CyHex Me Me H Me SbF₆ 80 Et Et n-Pr n-Pr Me Me H MeSbF₆ 81 Et Et Me Me Me Me H Me SbF₆ 82 n-Pr n-Pr i-Pr i-Pr Me Me H MeSbF₆ 83 n-Pr n-Pr tert-Bu tert-Bu Me Me H Me SbF₆ 84 n-Pr n-Pr NeoPenNeoPen Me Me H Me SbF₆ 85 n-Pr n-Pr CyHex CyHex Me Me H Me SbF₆ 86 n-Prn-Pr Me Me Me Me H Me SbF₆ 87 1-Ada 1-Ada i-Pr i-Pr Me Me H Me SbF₆ 881-Ada 1-Ada tert-Bu tert-Bu Me Me H Me SbF₆ 89 1-Ada 1-Ada NeoPen NeoPenMe Me H Me SbF₆ 90 1-Ada 1-Ada Me Me Me Me H Me SbF₆ 91 1-Ada 1-Ada EtEt Me Me H Me SbF₆ 92 1-Ada 1-Ada n-Pr n-Pr Me Me H Me SbF₆ 93 HIPT HIPTi-Pr i-Pr Me Me H Me SbF₆ 94 HIPT HIPT tert-Bu tert-Bu Me Me H Me SbF₆95 HIPT HIPT NeoPen NeoPen Me Me H Me SbF₆ 96 HIPT HIPT Me Me Me Me H MeSbF₆ 97 HIPT HIPT Et Et Me Me H Me SbF₆ 98 HIPT HIPT n-Pr n-Pr Me Me HMe SbF₆ 99 Biph Biph i-Pr i-Pr Me Me H Me SbF₆ 100 Biph Biph tert-Butert-Bu Me Me H Me SbF₆ 101 Biph Biph NeoPen NeoPen Me Me H Me SbF₆ 102Biph Biph Me Me Me Me H Me SbF₆ 103 i-Pr i-Pr i-Pr i-Pr Me Me H Me BArF₄104 i-Pr tert-Bu i-Pr i-Pr Me Me H Me BArF₄ 105 i-Pr i-Pr tert-Bu i-PrMe Me H Me BArF₄ 106 i-Pr tert-Bu i-Pr tert-Bu Me Me H Me BArF₄ 107 i-Pri-Pr tert-Bu tert-Bu Me Me H Me BArF₄ 108 i-Pr i-Pr NeoPen NeoPen Me MeH Me BArF₄ 109 i-Pr i-Pr CyHex CyHex Me Me H Me BArF₄ 110 i-Pr i-Pr MeMe Me Me H Me BArF₄ 111 i-Pr i-Pr Et Et Me Me H Me BArF₄ 112 tert-Butert-Bu i-Pr i-Pr Me Me H Me BArF₄ 113 tert-Bu tert-Bu tert-Bu tert-BuMe Me H Me BArF₄ 114 tert-Bu tert-Bu NeoPen NeoPen Me Me H Me BArF₄ 115tert-Bu tert-Bu CyHex CyHex Me Me H Me BArF₄ 116 tert-Bu tert-Bu Me MeMe Me H Me BArF₄ 117 tert-Bu tert-Bu Et Et Me Me H Me BArF₄ 118 tert-Butert-Bu n-Pr n-Pr Me Me H Me BArF₄ 119 NeoPen NeoPen i-Pr i-Pr Me Me HMe BArF₄ 120 NeoPen NeoPen tert-Bu tert-Bu Me Me H Me BArF₄ 121 NeoPenNeoPen NeoPen NeoPen Me Me H Me BArF₄ 122 NeoPen NeoPen CyHex CyHex MeMe H Me BArF₄ 123 NeoPen NeoPen Me Me Me Me H Me BArF₄ 124 CyHex CyHexi-Pr i-Pr Me Me H Me BArF₄ 125 CyHex CyHex tert-Bu tert-Bu Me Me H MeBArF₄ 126 CyPen CyPen i-Pr i-Pr Me Me H Me BArF₄ 127 CyPen CyPen tert-Butert-Bu Me Me H Me BArF₄ 128 Me Me i-Pr i-Pr Me Me H Me BArF₄ 129 Me Metert-Bu tert-Bu Me Me H Me BArF₄ 130 Et Et i-Pr i-Pr Me Me H Me BArF₄131 Et Et tert-Bu tert-Bu Me Me H Me BArF₄ 132 n-Pr n-Pr i-Pr i-Pr Me MeH Me BArF₄ 133 n-Pr n-Pr tert-Bu tert-Bu Me Me H Me BArF₄ 134 1-Ada1-Ada i-Pr i-Pr Me Me H Me BArF₄ 135 1-Ada 1-Ada tert-Bu tert-Bu Me Me HMe BArF₄ 136 i-Pr i-Pr i-Pr i-Pr Me Me H Me BF₄ 137 i-Pr i-Pr tert-Butert-Bu Me Me H Me BF₄ 138 i-Pr i-Pr NeoPen NeoPen Me Me H Me BF₄ 139i-Pr i-Pr CyHex CyHex Me Me H Me BF₄ 140 i-Pr i-Pr Me Me Me Me H Me BF₄141 tert-Bu tert-Bu i-Pr i-Pr Me Me H Me BF₄ 142 tert-Bu tert-Bu tert-Butert-Bu Me Me H Me BF₄ 143 tert-Bu tert-Bu NeoPen NeoPen Me Me H Me BF₄144 tert-Bu tert-Bu CyHex CyHex Me Me H Me BF₄ 145 tert-Bu tert-Bu Me MeMe Me H Me BF₄ 146 NeoPen NeoPen i-Pr i-Pr Me Me H Me BF₄ 147 NeoPenNeoPen tert-Bu tert-Bu Me Me H Me BF₄ 148 NeoPen NeoPen NeoPen NeoPen MeMe H Me BF₄ 149 CyHex CyHex i-Pr i-Pr Me Me H Me BF₄ 150 Me Me i-Pr i-PrMe Me H Me BF₄ 151 Et Et tert-Bu tert-Bu Me Me H Me BF₄ 152 1-Ada 1-Adai-Pr i-Pr Me Me H Me BF₄ 153 i-Pr i-Pr tert-Bu tert-Bu Me Me H Me PF₆154 i-Pr i-Pr NeoPen NeoPen Me Me H Me PF₆ 155 tert-Bu tert-Bu i-Pr i-PrMe Me H Me PF₆ 156 tert-Bu tert-Bu NeoPen NeoPen Me Me H Me PF₆ 157NeoPen NeoPen i-Pr i-Pr Me Me H Me PF₆ 158 NeoPen NeoPen tert-Bu tert-BuMe Me H Me PF₆ 159 CyHex CyHex i-Pr i-Pr Me Me H Me PF₆ 160 Me Me i-Pri-Pr Me Me H Me PF₆ 161 Et Et tert-Bu tert-Bu Me Me H Me PF₆ 162 1-Ada1-Ada i-Pr i-Pr Me Me H Me PF₆ 163 i-Pr i-Pr tert-Bu tert-Bu Me Me H MeArF 164 i-Pr i-Pr NeoPen NeoPen Me Me H Me ArF 165 tert-Bu tert-Bu i-Pri-Pr Me Me H Me ArF 166 tert-Bu tert-Bu NeoPen NeoPen Me Me H Me ArF 167NeoPen NeoPen i-Pr i-Pr Me Me H Me ArF 168 NeoPen NeoPen tert-Bu tert-BuMe Me H Me ArF 169 CyHex CyHex i-Pr i-Pr Me Me H Me ArF 170 Me Me i-Pri-Pr Me Me H Me ArF 171 Et Et tert-Bu tert-Bu Me Me H Me ArF 172 1-Ada1-Ada i-Pr i-Pr Me Me H Me ArF

In the case where neither of R¹¹ nor R¹² exists in formula (VI) (i.e.there is no substituent of R¹¹ or R¹² in either of the benzene rings),specific examples of the organometallic compounds represented by thefollowing formula (VIa) are shown in Table II.

The symbols in Table II have the same meanings as those in Table I.

TABLE II Compound R No. 1a 1b 2a 2b X 201 i-Pr i-Pr i-Pr i-Pr SbF₆ 202i-Pr tert-Bu i-Pr i-Pr SbF₆ 203 i-Pr i-Pr tert-Bu i-Pr SbF₆ 204 i-Prtert-Bu i-Pr tert-Bu SbF₆ 205 i-Pr tert-Bu tert-Bu tert-Bu SbF₆ 206 i-Pri-Pr tert-Bu tert-Bu SbF₆ 207 i-Pr i-Pr NeoPen NeoPen SbF₆ 208 i-Prtert-Bu NeoPen NeoPen SbF₆ 209 i-Pr i-Pr i-Pr NeoPen SbF₆ 210 i-Pr i-PrCyHex CyHex SbF₆ 211 i-Pr i-Pr Me Me SbF₆ 212 i-Pr i-Pr Et Et SbF₆ 213i-Pr i-Pr n-Pr n-Pr SbF₆ 214 tert-Bu tert-Bu i-Pr i-Pr SbF₆ 215 tert-Butert-Bu tert-Bu tert-Bu SbF₆ 216 tert-Bu tert-Bu tert-Bu i-Pro SbF₆ 217tert-Bu tert-Bu NeoPen NeoPen SbF₆ 218 tert-Bu tert-Bu CyHex CyHex SbF₆219 tert-Bu tert-Bu CyPen CyPen SbF₆ 220 tert-Bu tert-Bu Me Me SbF₆ 221tert-Bu tert-Bu Et Et SbF₆ 222 tert-Bu tert-Bu n-Pr n-Pr SbF₆ 223 NeoPenNeoPen i-Pr i-Pr SbF₆ 224 NeoPen NeoPen tert-Bu tert-Bu SbF₆ 225 NeoPenNeoPen NeoPen NeoPen SbF₆ 226 NeoPen NeoPen CyHex CyHex SbF₆ 227 NeoPenNeoPen Me Me SbF₆ 228 NeoPen NeoPen Et Et SbF₆ 229 NeoPen NeoPen n-Prn-Pr SbF₆ 230 CyHex CyHex i-Pr i-Pr SbF₆ 231 CyHex CyHex tert-Bu tert-BuSbF₆ 232 CyHex CyHex NeoPen NeoPen SbF₆ 233 CyHex CyHex Me Me SbF₆ 234CyPen CyPen i-Pr i-Pr SbF₆ 235 CyPen CyPen tert-Bu tert-Bu SbF₆ 236 MeMe i-Pr i-Pr SbF₆ 237 Me Me tert-Bu tert-Bu SbF₆ 238 Me Me NeoPen NeoPenSbF₆ 239 Me Me CyHex CyHex SbF₆ 240 Et Et i-Pr i-Pr SbF₆ 241 Et Ettert-Bu tert-Bu SbF₆ 242 Et Et NeoPen NeoPen SbF₆ 243 Et Et Me Me SbF₆244 n-Pr n-Pr i-Pr i-Pr SbF₆ 245 n-Pr n-Pr tert-Bu tert-Bu SbF₆ 246 n-Prn-Pr NeoPen NeoPen SbF₆ 247 n-Pr n-Pr CyHex CyHex SbF₆ 248 1-Ada 1-Adai-Pr i-Pr SbF₆ 249 1-Ada 1-Ada tert-Bu tert-Bu SbF₆ 250 1-Ada 1-AdaNeoPen NeoPen SbF₆ 251 1-Ada 1-Ada Me Me SbF₆ 252 1-Ada 1-Ada Et Et SbF₆253 HIPT HIPT i-Pr i-Pr SbF₆ 254 HIPT HIPT tert-Bu tert-Bu SbF₆ 255 HIPTHIPT NeoPen NeoPen SbF₆ 256 HIPT HIPT Me Me SbF₆ 257 Biph Biph i-Pr i-PrSbF₆ 258 Biph Biph tert-Bu tert-Bu SbF₆ 259 Biph Biph NeoPen NeoPen SbF₆260 Biph Biph Me Me SbF₆ 261 i-Pr i-Pr i-Pr i-Pr BArF₄ 262 i-Pr i-Prtert-Bu tert-Bu BArF₄ 263 i-Pr i-Pr NeoPen NeoPen BArF₄ 264 i-Pr i-PrCyHex CyHex BArF₄ 265 i-Pr i-Pr Me Me BArF₄ 266 i-Pr i-Pr Et Et BArF₄267 tert-Bu tert-Bu i-Pr i-Pr BArF₄ 268 tert-Bu tert-Bu tert-Bu tert-BuBArF₄ 269 tert-Bu tert-Bu NeoPen NeoPen BArF₄ 270 tert-Bu tert-Bu CyHexCyHex BArF₄ 271 tert-Bu tert-Bu Me Me BArF₄ 272 tert-Bu tert-Bu Et EtBArF₄ 273 tert-Bu tert-Bu n-Pr n-Pr BArF₄ 274 NeoPen NeoPen i-Pr i-PrBArF₄ 275 NeoPen NeoPen tert-Bu tert-Bu BArF₄ 276 NeoPen NeoPen NeoPenNeoPen BArF₄ 277 NeoPen NeoPen CyHex CyHex BArF₄ 278 NeoPen NeoPen Me MeBArF₄ 279 CyHex CyHex i-Pr i-Pr BArF₄ 280 CyHex CyHex tert-Bu tert-BuBArF₄ 281 CyPen CyPen i-Pr i-Pr BArF₄ 282 CyPen CyPen tert-Bu tert-BuBArF₄ 283 Me Me i-Pr i-Pr BArF₄ 284 Me Me tert-Bu tert-Bu BArF₄ 285 EtEt i-Pr i-Pr BArF₄ 286 Et Et tert-Bu tert-Bu BArF₄ 287 n-Pr n-Pr i-Pri-Pr BArF₄ 288 n-Pr n-Pr tert-Bu tert-Bu BArF₄ 289 1-Ada 1-Ada i-Pr i-PrBArF₄ 290 1-Ada 1-Ada tert-Bu tert-Bu BArF₄ 291 i-Pr i-Pr i-Pr i-Pr BF₄292 i-Pr i-Pr tert-Bu tert-Bu BF₄ 293 i-Pr i-Pr NeoPen NeoPen BF₄ 294i-Pr i-Pr CyHex CyHex BF₄ 295 i-Pr i-Pr Me Me BF₄ 296 tert-Bu tert-Bui-Pr i-Pr BF₄ 297 tert-Bu tert-Bu tert-Bu tert-Bu BF₄ 298 tert-Butert-Bu NeoPen NeoPen BF₄ 299 tert-Bu tert-Bu CyHex CyHex BF₄ 300tert-Bu tert-Bu Me Me BF₄ 301 NeoPen NeoPen i-Pr i-Pr BF₄ 302 NeoPenNeoPen tert-Bu tert-Bu BF₄ 303 NeoPen NeoPen NeoPen NeoPen BF₄ 304 CyHexCyHex i-Pr i-Pr BF₄ 305 Me Me i-Pr i-Pr BF₄ 306 Et Et tert-Bu tert-BuBF₄ 307 1-Ada 1-Ada i-Pr i-Pr BF₄ 308 i-Pr i-Pr tert-Bu tert-Bu PF₆ 309i-Pr i-Pr NeoPen NeoPen PF₆ 310 tert-Bu tert-Bu i-Pr i-Pr PF₆ 311tert-Bu tert-Bu NeoPen NeoPen PF₆ 312 NeoPen NeoPen i-Pr i-Pr PF₆ 313NeoPen NeoPen tert-Bu tert-Bu PF₆ 314 CyHex CyHex i-Pr i-Pr PF₆ 315 MeMe i-Pr i-Pr PF₆ 316 Et Et tert-Bu tert-Bu PF₆ 317 1-Ada 1-Ada i-Pr i-PrPF₆ 318 i-Pr i-Pr tert-Bu tert-Bu ArF 319 i-Pr i-Pr NeoPen NeoPen ArF320 tert-Bu tert-Bu i-Pr i-Pr ArF 321 tert-Bu tert-Bu NeoPen NeoPen ArF322 NeoPen NeoPen i-Pr i-Pr ArF 323 NeoPen NeoPen tert-Bu tert-Bu ArF324 CyHex CyHex i-Pr i-Pr ArF 325 Me Me i-Pr i-Pr ArF 326 Et Et tert-Butert-Bu ArF 327 1-Ada 1-Ada i-Pr i-Pr ArF

The organometallic compounds represented by formulae (II) to (VI) of thepresent invention can be suitably used as a catalyst for polymerizingvinyl monomers. The catalyst composition containing the organometalliccompound represented by formulae (II) to (VI) of the present inventioncan be used for homopolymerization of non-polar olefins, as well ascopolymerization of non-polar olefins and polar olefins.

The organometallic compounds represented by formulae (II) to (VI) do notneed to be isolated and the reaction solution for preparing the same canbe used as it is as a catalyst composition for polymerization.

The catalyst composition of the present invention can be used forhomopolymerization of non-polar olefins. Non-polar olefins are selectedfrom, for example, α-olefins such as ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1,5-hexadiene, 1,7-octadiene, cyclopentadiene, norbornadiene; andcombination thereof. Suitable non-polar olefin may be ethylene.

The catalyst composition of the present invention can be used forcopolymerization of the above-mentioned non-polar olefins and polarolefins. The polar olefins to be used is at least one member selectedfrom the group consisting of vinyl ester such as vinyl formate, vinylacetate, vinyl n-propionate, vinyl butyrate, vinyl isobutyrate, vinylpivalate, vinyl versatate, vinyl 2-ethylhexanoate, vinyl benzoate andisopropenyl acetate; vinyl chloride; vinyl ether such as methyl vinylether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether,i-butyl vinyl ether, t-butyl vinyl ether and phenyl vinyl ether; acrylicester such as methyl acrylate, ethyl acrylate, n-propyl acrylate,n-butyl acrylate, dodecyl acrylate and phenyl acrylate; methacrylicester such as methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, n-butyl methacrylate, dodecyl methacrylate and phenylmethacrylate; and acrylonitrile.

In the present invention, polar olefin may be an allyl compoundcontaining a polar group. Examples of an allyl compound containing apolar group include allyl acetate, allyl trifluoroacetate, allylalcohol, allyl methyl ether, allyl ethyl ether, allyl n-propyl ether,allyl n-butyl ether, allyl t-butyl ether, allyl phenyl ether, allylchloride, allyl bromide, allylamine, allylamine hydrochloride,N-allylaniline, N-t-butoxycarbonyl-N-allylamine andN-benzyloxycarbonyl-N-allylamine.

In the present invention, polar-olefins may be vinyl ketone monomer.Examples of vinyl ketone include 1-pentadecene-3-one, 1-heptene-3-one,1-decene-3-one, 3-butene-2-one, 1-nonadecene-3-one, 1-octene-3-one,1-heptene-3-one, 1-hexene-3-one, 1-pentene-3-one and1-phenyl-2-propene-1-one.

In the present invention, polar olefins may be N-vinyl monomer. N-vinylmonomer may be selected from N-vinylpyrrolidone, N-vinylcaprolactam,N-vinylformamide; N-vinylacetamide; N-vinylphthalimide;N-methylvinylacetamide; N-vinylcaprolactam;5-ethyl-5-methyl-3-vinyl-hydantoin; N-vinyl pyrrolidone;5-methyl-5-phenyl-3-vinyl-hydantoin; N-vinylcarbazole;N,N-dimethylacrylamide; 5-pentamethylene-3-vinyl-hydantoin and the like.

In the present invention, polar olefin may be polar norbornene monomer,vinylphosphonate, and ester thereof.

Preferred polar olefins in the present inventions are vinyl acetate,vinyl benzoate, acrylonitrile, methyl vinyl ether, ethyl vinyl ether,butyl vinyl ether, allyl acetate, allyl trifluoroacetate, allyl alcohol,allyl methyl ether, allyl ethyl ether, allyl n-propyl ether, allyln-butyl ether, allyl t-butyl ether, allyl phenyl ether, allyl chloride,allyl bromide, allylamine, allylamine hydrochloride, N-allylaniline,N-t-butoxycarbonyl-N-allylamine and N-benzyloxycarbonyl-N-allylamine.

The method for producing copolymer of non-polar olefins and polarolefins of the present invention can be conducted at a temperature of30° C. or higher and 150° C. or lower. The polymerization pressure mayvary depending on the catalyst component activity and selected non-polarolefins and polar olefins. Typically, a gaseous monomer such as ethylenerequires high pressure. Polymerization pressure is 0.50 atmosphere orhigher and 200 atmosphere and lower.

Furthermore, the molar ratio of the polar olefin monomer to theorganometallic complex in the present invention is 20:1 to 500,000:1.With respect to a gaseous monomer under high pressure, especially at agiven pressure such as 400 psi or higher, the molar ratio of thenon-polar olefin to the organometallic complex in the present inventionmay be 5,000,000:1 or higher, for example, 6,000,000:1 or lower,8,000,000:1 or lower or even higher than that. In the polymerizationmethod of the present invention, the amount of the diluent is 0.0 orhigher and 10,000 or less when it is expressed as the diluent volume(ml) per millimole of the organometallic complex of the presentinvention.

The organometallic compound of the present invention can be used forpolymerization by allowing it to be supported on a carrier. There is noparticular limitation on the carrier in this case, and examples thereofinclude inorganic carriers such as silica gel and alumina, and organiccarriers such as polystyrene, polyethylene and polypropylene. Examplesof the method for supporting a metal complex include a physicaladsorption method by impregnating the support with a solution of themetal complex and drying it, and a method of supporting the metalcomplex by chemically bonding the metal complex and the support.

There is no particular limitation on a polymerization method, and thepolymerization can be performed by a generally-used method. That is, aprocess method such as a solution polymerization method, suspensionpolymerization method and gas phase polymerization method are available.Particularly preferred are a solution polymerization method and asuspension polymerization method. The polymerization style can be eitherof batch polymerization or continuous polymerization. Also, thepolymerization can be conducted either by single-stage polymerization ormultistage polymerization.

The polymerization time can be appropriately adjusted depending on theprocessing mode and the polymerization activity of the catalyst, and canbe as short as several minutes or as long as several thousand hours.

It is preferable to fill the atmosphere in the polymerization systemwith an inert gas such as nitrogen and argon to prevent components otherthan monomers such as air, oxygen and moisture being mixed into theatmosphere to retain the catalytic activity. In the case of the solutionpolymerization, an inert solvent may be used in addition to monomers.There are no particular limitations on the inert solvent, and examplesinclude aliphatic hydrocarbon such as pentane, hexane and heptane;alicyclic hydrocarbon such as cyclopentane, cyclohexane andcycloheptane; aromatic hydrocarbon such as benzene, toluene and xylene;halogenated aliphatic hydrocarbon such as chloroform, methylenechloride, carbon tetrachloride, dichloroethane and tetrachloroethane;halogenated aromatic hydrocarbon such as chlorobenzene, dichlorobenzeneand trichlorobenzene; aliphatic ester such as methyl acetate and ethylacetate; and aromatic ester such as methyl benzoate and ethyl benzoate.

After completion of the polymerization reaction, the (co)polymer as areaction product is to be isolated by post-treatment using a knownoperation and treating method (e.g. neutralization, extraction withsolvents, washing with water, liquid separation, distillation withsolvents and reprecipitation).

EXAMPLES

Hereinafter, the present invention is described in greater detail byreferring to Examples described below. The present invention is by nomeans limited thereto. The measuring methods used in Synthesis Examples,Examples and Comparative Examples are as described below.

[Identification of the Organometallic Compound]

¹H-NMR, ¹³C-NMR and ³¹P-NMR spectra were measured using nuclear magneticresonance apparatus (JNM-ECP500 and JNMECS400 manufactured by JEOLLtd.). The content of the polar monomer unit in the polymer and thebranching degree of the copolymer were determined by analyzing ¹³C-NMRspectrum and adding Cr(acac)₃ (acac=Acetylacetonate; CH₃COCHCOCH₃) asrelaxation agent. A molecular weight was calculated by size exclusionchromatography in which polystyrene was employed as an internal standardsubstance using HLC-8121GPC/HT, manufactured by Tosoh Corporation,provided with TSK gel GMHHR-H(S)HT. The result was adjusted by applyingMark-Houwink parameters for polystyrene (K=1.75×10⁻² cm³/g, α=0.67) andlinear low-density polyethylene (K=5.90×10⁻² cm³/g, α=0.69). Theelemental analysis was conducted at Microanalytical Laboratory,Department of Chemistry, Graduate School of Science, the University ofTokyo. The high-resolution mass spectrometry (HRMS) was conducted by theelectrospray ionization time-of-flight (ESI-TOF) method using TSK gelJMS-T100LP manufactured by JEOL Ltd. in which polyethylene glycol wasemployed as an internal standard substance.

Synthesis Examples 1 to 4

The following compounds 1 to 4 were synthesized according to thefollowing scheme 1.

Compound 1: R¹=Ph, R²=Ph

Compound 2: R¹=Ph, R²=t-BuCompound 3: R¹=i-Pro, R²=PhCompound 4: R¹=i-Pro, R²=t-Bu (corresponding to Compound No. 11 in TableI)

Synthesis Example 1 Synthesis of Compound 1([methylpalladium(1-diphenylphosphino-2-diphenylphosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate])

As free BPMO (bisphosphine monoxide), after mixing a methylene chloride(2 ml) solution ofo-(Ph₂P)C₆H₄(P(O)Ph₂)(1-diphyenylphosphino-2-dihenylphosphinylbenzene)(139 mg, 0.301 mmol) and a methylene chloride (2 ml) solution of(cod)PdMeCl (cod=1,5-cyclooctadiene; 80 mg, 0.30 mmol) for five minutesat 25° C., toluene and hexane were added to the mixture to therebyobtain 175 mg of ((o-(Ph₂P)C₆H₄(P(O)Ph₂)PdMeCl complex as anintermediate. The solid and 2,6-lutidine (0.033 ml, 0.28 mmol) weredissolved in 5 ml of methylene chloride and reacted with silverhexafluoroantimonate (97 mg, 0.28 mmol) at 25° C. for ten minutes. Afterremoving silver chloride by Celite filtration, solvent was distilledaway. The resultant was dissolved in trifluoromethyl benzene and etherwas added thereto. The precipitate formed was collected and dried, andrecrystallized from methylene chloride to thereby obtain 175 mg ofCompound 1 in the paragraph title as a pale orange crystals which werestable in air and in humid condition. The yield was 49%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 7.76-7.70 (m, 2H), 7.61-7.29 (m, 20H),7.24-7.19 (m, 5H), 3.16 (s, 6H), 0.15 (d, J=3.7 Hz, 3H); ¹³C-NMR(CD₂Cl₂, 102 MHz) δ 139.59, 136.73 (dd, J=64, 10 Hz), 134.51 (d, J=12Hz), 134.05-133.76 (m), 132.60 (d, J=11 Hz), 132.01, 131.45 (d, J=12Hz), 129.64-129.41 (m), 128.70, 128.46, 128.17, 123.66 (d, J=9 Hz),26.94, −0.84; ³¹P NMR (CD₂Cl₂, 202 MHz) δ 40.42 (d, J=17 Hz), 29.52 (d,J=17 Hz); ¹⁹F NMR (CD₂Cl₂, 470 MHz) δ −113.93-134.61 (m); HRMS-ESI(m/z): [M]⁺ Calc'd for C₃₈H₃₆NOP₂Pd: 690.1307. Found: 690.1313.

Synthesis Example 2 Synthesis of Compound 2([methylpalladium(1-diphenylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate])

Compound 2 was obtained in the same way as in the case of Compound 1except that o-(Ph₂P)C₆H₄(P(O)t-Bu₂) was used as free BPMO. The yield was57%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 7.82-7.78 (m, 1H), 7.74 (t, J=7.8 Hz, 2H),7.64 (t, J=7.8 Hz, 1H), 7.58-7.50 (m, 10H), 7.44 (m, 1H), 7.28 (d, J=7.8Hz, 2H), 3.14 (s, 6H), 1.08 (d, J=14.4 Hz, 18H), 0.16 (d, J=3.0 Hz, 3H);¹³C-NMR (CD₂Cl₂, 102 MHz) δ 158.95, 139.59, 138.38 (dd, J=8, 3 Hz),134.54 (d, J=12 Hz), 134.21-133.28 (m), 132.59 (dd, J=7, 3 Hz), 132.01(d, J=2 Hz), 130.88 (dd, J=12, 2 Hz), 130.01, 129.61 (d, J=11 Hz),129.50, 123.63 (d, J=4 Hz), 37.95 (d, J=58 Hz), 27.26, 27.00, −2.25; ³¹PNMR (CD₂Cl₂, 202 MHz) δ 62.36, 35.49; Anal. Calc'd for C₃₄H₄₄F₆NOP₂PdSb:C, 46.05; H, 5.00; N, 1.58. Found: C, 45.86; H, 5.28; N, 1.37.

Synthesis Example 3 Synthesis of Compound 3([methylpalladium(1-diisopropylphosphino-2-diphenylphosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate])

Compound 3 was obtained in the same way as in the case of Compound 1except that o-(i-Pr₂P)C₆H₄(P(O)Ph₂) was used as free BPMO. The yield was49%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 8.05 (dt, J=7.4, 4.4 Hz, 1H), 7.79 (dt,J=7.6, 0.9 Hz, 1H), 7.72-7.65 (m, 3H), 7.57-7.49 (m, 5H), 7.34-7.29 (m,4H), 7.25 (dddd, J=15.1, 7.9, 3.4, 1.1 Hz, 1H), 7.14 (d, J=7.8 Hz 2H),2.66 (s, 6H), 1.41 (dd, J=15.1, 6.9 Hz, 6H), 1.27 (d, J=17.6, 7.1 Hz,6H), 0.33 (d, J=2.3 Hz, 3H); ¹³C-NMR (CD₂Cl₂, 102 MHz) δ 158.99, 139.38,136.48 (dd, J=15, 9 Hz), 134.58 (d, J=10 Hz), 134.73 (dd, J=100, 12.5Hz), 134.25 (d, J=3 Hz), 133.21 (dd, J=6, 3 Hz), 132.91 (d, J=11 Hz),131.27 (d, J=6 Hz), 131.11, 130.23, 129.73 (d, J=13 Hz), 123.45 (d, J=3Hz), 27.17 (d, J=26 Hz), 26.27, 19.62 (d, J=4 Hz), 18.86, −6.33 (d, J=4Hz); ³¹P NMR (CD₂Cl₂, 202 MHz) δ 42.74 (d, J=9 Hz), 42.23 (d, J=9 Hz);Anal. Calc'd for C₃₂H₄₀F₆NOP₂PdSb: C, 44.75; H, 4.69; N, 1.63. Found: C,44.55; H, 4.69; N, 1.52.

Synthesis Example 4 Synthesis of Compound 4([methylpalladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate])

Compound 4 was obtained in the same way as in the case of Compound 1except that o-(i-Pr₂P)C₆H₄(P(O)t-Bu₂) was used as free BPMO. The yieldwas 72%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 8.04 (dt, J=7.7 Hz, 3.9 Hz, 1H), 7.80-7.71(m, 4H), 7.26 (d, J=7.8 Hz, 2H), 3.14 (s, 6H), 2.73-2.65 (m, 2H),1.35-1.29 (m, 12H), 1.22 (d, J=14.4 Hz, 18H), 0.39 (d, J=2.1 Hz, 3H);¹³C-NMR (CDCl₃, 102 MHz) δ 158.75, 139.38, 135.20 (d, J=9 Hz), 134.47(d, J=12 Hz), 133.32-133.11 (m), 132.29 (dd, J=6, 3 Hz), 130.52 (d, J=12Hz), 123.62 (d, J=3 Hz), 38.27 (d, J=57 Hz), 29.01 (d, J=26 Hz), 27.80,26.91, 20.13 (d, J=4 Hz), 19.47, −8.11; ³¹P NMR (CD₂Cl₂, 202 MHz) δ58.22, 44.85; Anal. Calc'd for C₂₈H₄₈F₆NOP₂PdSb: C, 41.07; H, 5.91; N,1.71. Found: C, 40.90; H, 5.96; N, 1.65.

Synthesis Examples 5 to 6

Next, Compounds 5 to 6 were synthesized according to the followingscheme 2.

Compound 5: X=SbF₆ (corresponding to Compound No. 206 in Table II)Compound 6: X=BArF₄ (corresponding to Compound No. 262 in Table II)

Compound A (acetanilide palladium chloride dimer) was synthesizedaccording to the method described in a literature (Chem. Eur. J. 2010,16, 4010-4017).

Synthesis Example 5 Synthesis of Compound 5([κ2-(o-acetanilide)palladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate]

o-(i-Pr₂P)C₆H₄ (P(O)t-Bu₂) (142 mg, 0.401 mmol) as free BPMO andCompound A (110 mg, 0.199 mmol) were dissolved in 7 ml of methylenechloride and stirred at 25° C. for three hours. The solution was pouredslowly into silver hexafluoroantimonate (0.31 g, 0.90 mmol) in a flaskcooled to −78° C. After vigorous stirring at 25° C. for 30 minutes, theresultant solution was condensed by removing silver chloride throughCelite filtration. Toluene was poured into the solution to obtainprecipitate. The precipitate was recrystallized from methylene chlorideto thereby obtain Compound 5 as a pale orange crystals which were stablein air and humid condition. The yield was 73%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 8.96 (s, 1H), 8.00-7.97 (m, 1H), 7.81-7.72(m, 3H), 7.24 (ddd, J=7.7, 4.7, 1.1 Hz, 1H), 7.09 (t, J=7.1 Hz, 1H),6.98-6.92 (m, 2H), 2.41 (s, 3H), 1.42 (d, J=14.4 Hz, 18H), 1.22 (dd,J=15.4, 7.1 Hz, 6H), 1.03 (dd, J=18.3, 7.1 Hz, 6H); ¹³C-NMR (CD₂Cl₂, 102MHz) δ 172.55 (d, J=3 Hz), 138.26 (d, J=7 Hz), 135.80 (d, J=9 Hz),135.12, 134.36 (d, J=11 Hz), 133.35 (dd, J=13, 8 Hz), 132.17 (dd, J=6, 3Hz), 131.46 (dd, J=33, 4 Hz), 130.73 (dd, J=12, 2 Hz), 126.49, 125.51(d, J=4 Hz), 125.19 (d, J=2 Hz), 118.50, 38.04 (d, J=57 Hz), 27.83,27.76 (d, J=24 Hz), 22.49 (d, J=4 Hz), 19.99 (d, J=4 Hz), 19.28; ³¹P NMR(CD₂Cl₂, 202 MHz) δ 63.07, 52.30; Anal. Calc'd for C₂₈H₄₄F₆NOP₂PdSb: C,40.48; H, 5.34; N, 1.69. Found: C, 40.20; H, 5.41; N, 1.53.

Example 6 Synthesis of Compound 6([2-(o-acetanilide)palladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenylborate]

Compound 6 was obtained in the same way as in the case of Compound 5except that NaBArF₄ was used instead of silver hexafluoroantimonate. Theyield was 96%.

¹H NMR (CD₂Cl₂, 500 MHz) δ 8.27 (s, 1H), 7.98-7.94 (m, 1H), 7.87-7.69(m, 11H), 7.56 (s, 4H), 7.26 (ddd, J=7.8, 4.6, 1.1 Hz, 1H), 7.12 (t,J=7.8 Hz, 1H), 7.00 (t, J=7.8 Hz, 1H), 6.82 (dd, J=7.8, 1.4 Hz, 1H),2.80-2.73 (m, 2H), 2.40 (s, 3H), 1.41 (d, J=14.4 Hz, 18H), 1.21 (dd,J=15.4, 6.9 Hz, 6H), 1.01 (dd, J=18.3, 7.1 Hz, 6H); ¹³C-NMR (CDCl₃, 102MHz) δ 172.34 (d, J=3 Hz), 162.40 (q, J=50 Hz), 138.59 (d, J=7 Hz),135.74 (d, J=10 Hz), 135.42, 135.18 (d, J=12 Hz), 134.82, 134.45 (d,J=11 Hz), 133.42 (dd, J=13, 8 Hz), 132.21 (dd, J=6, 3 Hz), 131.27 (dd,J=34, 4 Hz), 130.83 (dd, J=12, 2 Hz), 129.51 (qq, J=32, 3 Hz), 126.66,126.02 (d, J=4 Hz), 125.30 (d, J=2 Hz), 125.21 (q, J=272 Hz), 118.15,38.12 (d, J=58 Hz), 27.80, 27.75 (d, J=25 Hz), 22.88 (d, J=3 Hz), 19.93(d, J=4 Hz), 19.24; ³¹P NMR (CD₂Cl₂, 202 MHz) δ 63.03, 52.65; ¹⁹F NMR(CD₂Cl₂, 470 MHz) 6-62.73; Anal. Calc'd for C₆₀H₅₆BF₂₄NO₂P₂Pd: C, 49.42;H, 3.87; N, 0.96. Found: C, 49.18; H, 4.09; N, 0.84.

Synthesis Example 7 Synthesis of Compound 7([methylpalladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]

Compound 7 was synthesized using Compound 4 as a raw material. That is,a methylene chloride suspension (8 ml) of([methylpalladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][hexafluoroantimonate)(Compound 4; 0.24 g; 0.30 mmol) andsodium[tetrakis(3,5-bis(trifluoromethyl)phenyl]borate (0.26 g, 0.30mmol) was stirred at room temperature for 20 minutes under argonatmosphere. The reaction solution was filtered through a pad of Celite(dried diatom) and the filtrate was subjected to vacuum concentration.The yellow solid residue was washed with hexane, and dried under reducedpressure to obtain 0.14 g of Compound 7. The yield was 95%.

¹H NMR (CDCl₃) δ 7.97 (td, J=7.6, 3.7 Hz, 1H), 7.71 (s, 8H), 7.68-7.59(m, 4H), 7.51 (s, 4H), 7.17 (d, J=7.5 Hz, 2H), 3.09 (s, 6H), 2.66-2.57(m, 2H), 1.30-1.25 (m, 12H), 1.16 (d, J=14.5 Hz, 18H), 0.37 (d, J=2.0Hz, 3H); ³¹P NMR (202 MHz, CDCl₃) δ 58.20, 44.83.

Synthesis Example 8 Synthesis of Compound 7([methylpalladium(1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]

Compound 7 was synthesized using Compound 8 represented by the followingformula, which is an intermediate in the synthesis of Compound 4 inSynthesis Example 4, as a material.

That is, a methylene chloride suspension (8 ml) ofchloromethylpalladium[1-diisopropylphosphino-2-di(t-butyl)phosphinylbenzene](Compound 8; 0.10 g; 0.20 mmol), sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (0.18 g, 0.20 mmol) and2,6-dimethylpyridine (0.021 g, 0.20 mmol) was stirred at roomtemperature for 20 minutes under argon atmosphere. The reaction mixturewas filtered through a pad of Celite (dried diatom) and the filtrate wassubjected to vacuum concentration. The yellow solid residue was washedwith hexane, and dried under reduced pressure to obtain 0.26 g ofCompound 7. The yield was 90%. The ¹H- and ³¹P-NMR spectra of Compound 7were coincident with those described in Synthesis Example 7.

Synthesis Examples 9 to 12

Compounds 9 to 12 were synthesized according to the following reactionscheme.

Synthesis Example 9 Synthesis of Compound 9(chloromethylpalladium[1-bis(o-methoxyphenyl)phosphino-2-di(t-butyl)phosphinylbenzene])

The reaction solution between the THF solution (14 ml) of 2-bromoanisole(0.34 g, 2.0 mmol) and n-butyllithium (2.1 mmol in 1.64 M pentanesolution; 1.3 ml) was added to the THF solution (7 ml) of Compound 9b(0.37 g, 1.0 mmol) synthesized from lithiateddi(t-butyl)phenylphosphineoxide and phosphorus trichloride at −78° C.and stirred for 30 minutes under argon atmosphere. After slowly raisingthe solution temperature to room temperature, the solution was stirredat room temperature for one hour. The reaction was terminated withwater, and after subjecting the reaction solution to vacuumconcentration, the residue was dissolved in methylene chloride and theresultant solution was filtered through a pad of Celite. Afterdistilling away the solvent, a purification operation was performedthrough silica gel-column chromatography using methylenechloride/methanol (30:1) as an eluent and recrystallization fromTHF/hexane to thereby obtain 0.30 g of Compound 9a.

Furthermore, a methylene chloride solution (3 ml) of the obtainedCompound 9a (0.14 g, 0.30 mmol) and (cod)PdMeCl (0.088 g, 0.33 mmol) wasstirred at room temperature for one hour under argon atmosphere. Thereaction solution was filtered through a pad of Celite (dried diatomite)and the filtrate was subjected to vacuum concentration. The residue wassubjected to recrystallization from methylene chloride and diethyl etherto obtain 0.15 g of Compound 9. The yield was 81%.

¹H NMR (CD₂Cl₂) δ 8.68 (br s, 1H), 7.65-7.61 (m, 1H), 7.55-7.53 (m, 1H),7.50-7.48 (m, 3H), 7.40 (dd, J₁=J₂=7.7 Hz, 1H), 7.14 (dd, J=J₂=7.4 Hz,1H), 6.99 (dd, J=8.2, 5.5 Hz, 1H), 6.89 (dd, J₁=J₂=7.3 Hz, 1H), 6.80(dd, J=8.2, 3.4 Hz, 1H), 6.73 (dd, J=11.6, 7.4 Hz, 1H), 3.69 (s, 3H),3.41 (s, 3H), 1.45 (d, J=14.2 Hz, 9H), 1.09 (d, J=14.2 Hz, 9H), 0.13 (d,J=3.0 Hz, 3H); ³¹P NMR (202 MHz, CD₂Cl₂) δ 63.46 (s, P(O)t-Bu₂), 27.69(br s, PAr₂).

Synthesis Example 10 Synthesis of Compound 10([methylpalladium(1-bis(2-methoxyphenyl)phosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenylborate])

The methylene chloride suspension (2 ml) of Compound 9 (0.050 g, 0.078mmol), 2,6-dimethylpyridine (0.013 g, 0.12 mmol) and sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (0.069 g, 0.078 mmol) wasstirred under argon atmosphere at room temperature for one hour. Thereaction solution was filtered through a pad of Celite (dried diatomite)and the filtrate was subjected to vacuum concentration. The residue wassubjected to reprecipitation from methylene chloride and pentane toobtain 0.10 g of Compound 10. The yield was 83%.

¹H NMR (CD₂Cl₂) δ 8.30 (dd, J=15.4, 7.8 Hz, 1H), 7.72 (s, 8H), 7.64-7.57(m, 10H), 7.49 (dd, J=J₂=7.7 Hz, 1H), 7.23 (d, J=8.0 Hz, 1H), 7.19 (d,J=7.5 Hz, 1H), 7.14 (dd, J₁=J₂=7.4 Hz, 1H), 7.06 (dd, J=8.1, 5.6 Hz,1H), 6.93-6.90 (m, 2H), 6.68 (dd, J=11.7, 7.8 Hz, 1H), 3.76 (s, 3H),3.49 (s, 3H), 3.18 (s, 3H), 3.04 (s, 3H), 1.05 (d, J=14.2 Hz, 9H), 1.01(d, J=14.4 Hz, 9H), −0.01 (d, J=3.0 Hz, 3H); ³¹P NMR (202 MHz, CD₂Cl₂) δ63.07 (s, P(O)t-Bu₂), 25.90 (s, PAr′₂); Anal. Calc'd forC₆₈H₆₀BF₂₄NO₃P₂Pd: C, 51.88; H, 3.84; N, 0.89. Found: C, 51.69; H, 3.89;N, 0.71.

Synthesis Example 11 Synthesis of Compound 11(chloromethylpalladium[1-bis(2-methylphenyl)phosphino-2-di(t-butyl)phosphinylbenzene])

Compound 11 was synthesized in a similar manner to that described inSynthesis Example 9. That is, a methylene chloride solution (2 ml) ofCompound 11a (0.10 g, 0.22 mmol) synthesized from Compound 9a and(cod)PdMeCl (0.064 g, 0.24 mmol) was stirred at room temperature for onehour under argon atmosphere. The reaction solution was filtered througha pad of Celite (dried diatomite) and the filtrate was subjected tovacuum concentration. The residue was subjected to reprecipitation frommethylene chloride and diethyl ether to obtain 0.10 g of Compound 11.The yield was 74%.

¹H NMR (CDCl₃) δ 7.82-7.78 (m, 1H), 7.63 (dd, J₁=J₂=7.6 Hz, 1H), 7.51(dd, J₁=J₂=7.4 Hz, 1H), 7.42-7.35 (m, 4H), 7.26 (dd, J₁=J₂=7.9 Hz, 1H),7.19 (dd, J₁=J₂=7.2 Hz, 1H), 7.01 (dd, J₁=J₂=7.6 Hz, 1H), 6.66 (dd,J₁=J₂=9.4 Hz, 1H), 3.14 (s, 3H), 2.29 (s, 3H), 1.62 (d, J=14.2 Hz, 9H),1.07 (d, J=14.0 Hz, 9H), 0.54 (d, J=2.7 Hz, 3H); ³¹P NMR (202 MHz,CD₂Cl₂) δ 63.07 (s, P(O)t-Bu₂), 25.90 (s, PAr₂).

Synthesis Example 12 Synthesis of Compound 12([methylpalladium(1-bis(2-methylphenyl)phosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenylborate])

Compound 12 was synthesized in a similar manner to that described inSynthesis Example 7. That is, a methylene chloride suspension (3 ml) ofCompound 11 (0.082 g, 0.14 mmol), 2,6-dimethylpyridine (0.029 g, 0.27mmol) and sodium tetrakis[(3,5-bis(trifluoromethyl)phenyl]borate (0.12g, 0.14 mmol) was stirred at room temperature for 1.5 hour under argonatmosphere. The reaction mixture was filtered through a pad of Celite(dried diatom) and the filtrate was subjected to vacuum concentration.The residue was subjected to reprecipitation from methylene chloride andpentane to obtain 0.19 g of Compound 12. The yield was 90%.

¹H NMR (CD₂Cl₂) δ 7.79-7.46 (m, 21H), 7.32-7.30 (m, 2H), 7.22 (2H, t,J=7.2 Hz), 7.14-7.12 (m, 1H), 6.63 (dd, J=11.3, 8.1 Hz, 1H), 3.12 (s,3H), 3.09 (s, 3H), 2.94 (s, 3H), 2.28 (s, 3H), 1.04 (d, J=14.4 Hz, 9H),0.97 (d, J=14.7 Hz, 9H), 0.18 (d, J=2.7 Hz, 3H); ³¹P NMR (202 MHz,CD₂Cl₂) δ 64.25 (s, P(O)t-Bu₂), 27.37 (s, PAr′₂); Anal. Calc'd forC₆₈H₆₀BF₂₄NOP₂Pd: C, 52.95; H, 3.92; N, 0.91.

Found: C, 52.57; H, 3.94; N, 0.57.

Synthesis Examples 13 and 14

Compounds 13 and 14 were synthesized according to the following reactionscheme.

Synthesis Example 13 Synthesis of Compound 13(chloromethylpalladium[1-di(t-butyl)phosphino-2-dimethylphosphinylmethane])

A methylene chloride solution (10 ml) of Compound 13a, which isquantitatively obtained from the reaction ofdi(t-butyl)phosphinomethyllithium (0.083 g, 0.50 mmol) anddimethylphosphinic chloride (0.083 g, 0.50 mmol), and (cod)PdMeCl (0.13g, 0.50 mmol) was stirred at room temperature under argon atmosphere.The reaction solution was filtered through a pad of Celite (drieddiatomite) and the filtrate was subjected to vacuum concentration. Theresidue was subjected to purification through recrystallization frommethylene chloride and hexane to obtain 0.071 g of Compound 13. Theyield was 36%.

¹H NMR (CD₂Cl₂) δ 2.32 (dd, J₁=J₂=9.7 Hz, 2H), 1.78 (d, J=13.1 Hz, 6H),1.40 (d, J=14.7 Hz, 18H), 0.88 (d, J=2.3 Hz, 3H); ³¹P NMR (202 MHz,CD₂Cl₂) δ 52.40 (d, J=13.1 Hz), 50.83 (d, J=13.1 Hz).

Synthesis Example 14 Synthesis of Compound 14([methylpalladium(1-di(t-butyl)phosphino-2-dimethylphosphinylmethane)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate])

The methylene chloride suspension (3 ml) of Compound 13 (0.071 g, 0.18mmol), 2,6-dimethylpyridine (0.019 g, 0.18 mmol) and silverhexafluoroantimonate (0.062 g, 0.18 mmol) was stirred at roomtemperature under argon atmosphere. After the reaction mixture wasfiltered through a pad of Celite (dried diatomite), sodiumtetrakis(3,5-bis(trifluoromethyl)phenylborate (0.15 g, 0.18 mmol) wasadded to the filtrate and stirred again at room temperature under argonatmosphere. After the reaction mixture was filtered through a pad ofCelite (dried diatomite), the solvent of the filtrate was distilled awayto obtain 0.23 g of Compound 14. The yield was 96%.

¹H NMR (CD₂Cl₂) δ 7.74 (s, 8H), 7.66 (t, J=7.7 Hz, 1H), 7.57 (s, 4H),7.19 (d, J=7.8 Hz, 2H), 2.97 (s, 6H), 2.35 (dd, J₁=J₂=9.7 Hz, 2H), 1.70(d, J=12.8 Hz, 6H), 1.45 (d, J=14.9 Hz, 18H), 0.63 (d, J=2.1 Hz, 3H);³¹P NMR (C₆D₆) δ 58.01 (d, J=8.7 Hz), 53.25 (d, J=8.7 Hz).

Synthesis Examples 15 and 16

Compounds 15 and 16 were synthesized according to the following reactionscheme.

Synthesis Example 15 Synthesis of Compound 15(chloromethylpalladium[1-bis(2,4-dimethoxyphenyl)phosphino-2-di(t-butyl)phosphinylbenzene])

Compound 15 was synthesized in a similar manner to that in SynthesisExamples 9 and 11. That is, the reaction solution between the THFsolution (14 ml) of 1-bromo-2,4-dimethoxybenzene (0.43 g, 2.0 mmol) andn-butyllithium (2.1 mmol in 1.64 M pentane solution; 1.3 ml) was addedto the THF solution (7 ml) of Compound 9b (0.37 g, 1.0 mmol) synthesizedfrom lithiated di(t-butyl)phenylphosphineoxide and phosphorustrichloride at −78° C. and stirred for 30 minutes under argonatmosphere. After slowly raising the solution temperature to roomtemperature, the solution was stirred at room temperature for one hour.The reaction was terminated with water, and after subjecting thereaction solution to vacuum concentration, the residue was dissolved inmethylene chloride and the resultant solution was filtered through a padof Celite. After distilling away the solvent, a purification operationwas performed through recrystallization from methylene chloride/hexaneto thereby obtain 0.40 g of Compound 15a.

Furthermore, a methylene chloride solution (2 ml) of the obtainedCompound 15a (0.10 g, 0.18 mmol) and (cod)PdMeCl (0.054 g, 0.20 mmol)was stirred at room temperature for two hours under argon atmosphere.The reaction solution was filtered through a pad of Celite (drieddiatomite) and the filtrate was subjected to vacuum concentration. Theresidue was subjected to purification by recrystallization frommethylene chloride/diethyl ether to obtain 0.098 g of Compound 15. Theyield from Compound 9b was 55%.

¹H NMR (CD₂Cl₂) δ 8.75 (br s, 1H), 7.62-7.54 (m, 2H), 7.47-7.45 (m, 1H),7.38 (t, J=7.7 Hz, 1H), 6.68-6.63 (m, 2H), 6.49 (dd, J=4.1, 2.1 Hz, 1H),6.42 (d, J=8.5 Hz, 1H), 6.31 (t, J=2.3 Hz, 1H), 3.81 (d, J=2.7 Hz, 6H),3.65-3.63 (3H, m), 3.35 (3H, s), 1.46 (9H, d, J=14.2 Hz), 1.05 (9H, d,J=14.0 Hz), 0.16 (0.5H, d, J=3.2 Hz), 0.11 (2.5H, d, J=3.0 Hz); ³¹P NMR(202 MHz, CD₂Cl₂) δ 64.19 (s), 27.17 (br s).

Synthesis Example 16 Synthesis of Compound 16([methylpalladium(1-bis(2,4-dimethoxyphenyl)phosphino-2-di(t-butyl)phosphinylbenzene)(2,6-lutidine)][tetrakis(3,5-bis(trifluoromethyl)phenylborate])

Compound 16 was synthesized in a similar manner to that in SynthesisExamples 10 and 12. That is, the methylene chloride suspension (4 ml) ofCompound 15 (0.098 g, 0.14 mmol), 2,6-dimethylpyridine (0.023 g, 0.27mmol) and sodium tetrakis(3,5-bis(trifluoromethyl)phenyl]borate (0.12 g,0.14 mmol) was stirred at room temperature for 40 minutes under argonatmosphere. The residue was subjected to reprecipitation from methylenechloride and pentane to obtain 0.15 g of Compound 12. The yield was 66%.

¹H NMR (CD₂Cl₂) δ 8.34 (1H, dd, J=15.4, 8.7 Hz), 7.72 (t, J=2.2 Hz, 8H),7.65-7.52 (m, 8H), 7.47 (dd, J₁=J₂=7.7 Hz, 1H), 7.20 (d, J=7.6 Hz, 1H),7.17 (d, J=7.6 Hz, 1H), 6.66 (d, J=8.5 Hz, 1H), 6.62 (dd, J=11.7, 8.5Hz, 1H), 6.58 (dd, J=4.6, 2.3 Hz, 1H), 6.46 (d, J=8.5 Hz, 1H), 6.40 (dd,J₁=J₂=2.6 Hz, 1H), 3.84 (s, 3H), 3.82 (s, 3H), 3.71 (s, 3H), 3.44 (s,3H), 3.17 (s, 3H), 3.04 (s, 3H), 1.05 (d, J=14.2 Hz, 9H), 1.00 (d,J=14.4 Hz, 9H), −0.02 (d, J=3.0 Hz, 3H); ³¹P NMR (202 MHz, CD₂Cl₂) δ62.79 (s), 24.22 (s).

Homopolymerization of Ethylene

Examples 1 to 9

6.0 μmol (in 1.0 ml of 6.0 M methylene chloride solution) of each ofCompounds 1 to 6 (Examples 1-4, 6 and 8) and 0.75 μmol (in 1.0 ml of0.75 M methylene chloride solution) of each of Compounds 4 to 6(Examples 5, 7 and 9) were placed in the 50 ml-volume stainlessautoclave. After fully drying the autoclave at 120° C., it was cooled toroom temperature in a dryer to distil away the methylene chloride underreduced pressure. Toluene (15 ml) was added thereto to solve thecatalyst, and ethylene (3 MPa) was injected to allow the solutions toreact at 80° C. (or 100° C.) for one hour or three hours. The resultsare shown in Table 1.

TABLE 1 Molecular Molecular weight Catalyst Polymerization Activityweight (Mn) distribution (μmol) time (h) (kgmol⁻¹h⁻¹) (×10³) (Mw/Mn)Example 1 Compound 1 3 63 0.8 (1.8) 1.8 (6.0) Example 2 Compound 2 3 3616 (38) 2.5 (6.0) Example 3 Compound 3 1 130 0.9 (1.9) 1.8 (6.0) Example4 Compound 4 1 340 39 (91) 2.3 (6.0) Example 5*¹ Compound 4 1 1900 15(34) 2.6 (0.75) Example 6*² Compound 5 1 180 12 (27) 3.6 (6.0) Example7*¹ Compound 5 1 1300 25 (58) 1.9 (0.75) Example 8 Compound 6 1 350 39(92) 2.6 (6.0) Example 9*¹ Compound 6 1 2800 29 (69) 2.1 (0.75) *¹Thereaction was performed at 100° C. *²The reaction was performed in amixed solution of 1 ml of methylene chloride and 14 ml of toluene. *³Thevalue adjusted by applying Mark-Houwink parameters. The values inparentheses are the values in terms of polystyrene before theadjustment.

Table 1 shows that among Compounds 1 to 4, Compound 4, in which both ofphosphorus atoms are substituted with a branched alkyl group, gives ahigh-molecular-weight polymers as well as having very high catalyticactivity. Also, according to the quantitative analysis based on ¹³C-NMRspectrum, the polymer obtained by using Compound 4 had only about onemethyl branch per 1,000 carbon atoms, and a highly linear polyethylenewas obtained.

Compounds 5 and 6, in which a catalyst precursor had been changed, alsoshowed a very high catalytic activity.

The ¹³C-NMR spectrum chart of the product in Example 5 is shown in FIG.1.

Copolymerization of Ethylene and Vinyl Acetate

Example 10

Compound 4, toluene, ethylene (3 MPa) and vinyl acetate in amounts as inTable 2 were put in a stainless steel autoclave to perform apolymerization reaction at a temperature for a period of time asdescribed in the table.

The ¹³C-NMR spectrum chart of the product in Example 10 is shown in FIG.2.

Example 11

The catalyst was changed to Compound 6 and the polymerization reactionwas performed in a similar manner to that in Example 10 under conditionsas described in Table 2.

Although there have been few reports on coordination-insertionpolymerization using a comonomer with vinyl acetate, the progress ofcopolymerization was confirmed in both cases of using Compound 4 andusing Compound 6. The result of the quantitative analysis based on¹³C-NMR spectrum of the obtained polymer confirmed that a vinyl acetatemonomer was incorporated in both terminals of the polymer chain as wellas in the main chain.

Copolymerization of Ethylene and Allyl Acetate

Example 12

Compound 4, toluene, ethylene (3 MPa) and allyl acetate in amounts as inTable 2 were put in a stainless steel autoclave to perform apolymerization reaction at a temperature for a period of time asdescribed in the table.

The ¹³C-NMR spectrum chart of the product in Example 12 is shown in FIG.3.

Example 13

The catalyst was changed to Compound 6 and the polymerization reactionwas performed in a similar manner to that in Example 12 under conditionsas described in Table 2.

The progress of copolymerization of ethylene and allyl acetate wasconfirmed in both cases of using Compound 4 and using Compound 6. Themolecular weight (Mn) of the polymer obtained by using Compound 6 wasabout twice as much as that reported in the case of a catalyst ofphosphine-sulfonic acid ester ligand (J. Am. Chem. Soc. 2011, 133,1232).

Copolymerization of Ethylene and Allyl Chloride

Example 14

Compound 4, toluene, ethylene (3 MPa) and allyl chloride in amounts asin Table 2 were put in a stainless steel autoclave to perform apolymerization reaction at a temperature for a period of time asdescribed in the table. The ¹³C-NMR spectrum chart of the product inExample 14 is shown in FIG. 4.

Example 15

The catalyst was changed to Compound 6 and the polymerization reactionwas performed in a similar manner to that in Example 14 under conditionsas described in Table 2.

The progress of copolymerization of ethylene and allyl chloride wasconfirmed in both cases of using Compound 4 and using Compound 6. Theamount of the incorporated polar monomer was nearly equal to that in theabove-mentioned report on the catalyst of phosphine-sulfonic acid esterligands, and the molecular weight (Mn) of the polymer was about twice asmuch as that in the report.

Copolymerization of Ethylene and Acrylonitrile

Example 16

Compound 4, toluene, ethylene (3 MPa) and acrylonitrile in amounts as inTable 2 were put in a stainless steel autoclave to perform apolymerization reaction at a temperature for a period of time asdescribed in the table. The ¹³C-NMR spectrum chart of the product inExample 16 is shown in FIG. 5.

Example 17

The catalyst was changed to Compound 6 and the polymerization reactionwas performed in a similar manner to that in Example 16 under conditionsas described in Table 2.

The progress of copolymerization of ethylene and acrylonitrile wasconfirmed in both cases of using Compound 4 and using Compound 6. Theresult of the quantitative analysis based on ¹³C-NMR spectrum of theobtained polymers confirmed that acrylonitrile monomers wereincorporated in both terminals of the polymer chain as well as in themain chain, and the amount of the incorporated monomer was 2.0 to 2.5%.

Copolymerization of Ethylene and Butyl Vinyl Ether

Example 18

Compound 4, toluene, ethylene (3 MPa) and butyl vinyl ether in amountsas in Table 2 were put in a stainless steel autoclave to perform apolymerization reaction at a temperature for a period of time asdescribed in the table. The ¹³C-NMR spectrum chart of the product inExample 18 is shown in FIG. 6.

TABLE 2 Comono- Solvent Incorpo- Me Exam- Catalyst Comono- mer a- amountTempera- Reaction Yield Activity Mn Mw rated a- branch*⁴ ples (mmol) mermount (ml) (ml) ture (° C.) time (h) (g) (kgmol⁻¹h⁻¹) (×10³) (×10³)mount (%) (/10³C) 10 Compound Vinyl 12 3 80 15 0.21 0.72 3.4 2.5 1.3 1.54 (0.02) acetate 11 Compound Vinyl 12 3 80 16 0.18 1.1 3.0 2.5 1.4 1.7 6(0.01) acetate 12 Compound Allyl 3 12 80 12 0.18 1.4 17 2.7 1.0 1.0 4(0.01) acetate 13 Compound Allyl 3 12 80 12 0.94 7.6 35 2.2 1.2 0.7 6(0.01) acetate 14 Compound Allyl 3 12 80 20 0.12 0.31 13 1.9 1.1 1.0 4(0.02) chloride 15 Compound Allyl 3 12 80 20 0.18 0.93 20 2.9 0.7 0.6 6(0.01) chloride 16 Compound Acrylo- 2.5 2.5 100 86 0.50 0.58 3.5 2.4 2.11.8 4 (0.01) nitrile 17 Compound Acrylo- 2.5 2.5 100 72 0.30 0.69 3.52.7 2.5 0.1 6 (0.006) nitrile 18 Compound Butyl vinyl 5 10 80 21 0.280.66 21 1.9 2.0 1.4 4 (0.02) ether 19 Compound Butyl vinyl 5 10 80 200.23 1.2 19 2.4 4.1 0.5 6 (0.01) ether *⁴The number of methyl branchesper 1,000 carbon atoms in the polymer was determined by the quantitativeanalysis of ¹³C NMR spectrum.

Example 19

The catalyst was changed to Compound 6 and the polymerization reactionwas performed in a similar manner to that in Example 16 under conditionsas described in Table 2.

Although it has been considered the copolymerization of ethylene andvinyl ether is difficult with a conventional cationic α-diiminepalladium catalyst, the progress of copolymerization of ethylene andbutyl vinyl ether was confirmed in both cases of using Compound 4 andusing Compound 6.

Examples 20 to 24

The catalysts in Examples 1 to 9 were changed to Compounds 7, 10, 12 and14, and homopolyzation of ethylene was conducted in a similar manner.The polymerization conditions and the results are shown in Table 3 andTable 4, respectively.

TABLE 3 Ethylene Polymerization Exam- Catalyst pressure temperature Timeples (μmol) Solvent (ml) (MPa) (° C.) (h) 20 Compound 7 Toluene (15) 3.080 1 (6.0) 21 Compound 7 Toluene (15) 3.0 100 1 (0.75) 22 CompoundToluene (15) 3.0 100 1 10 (0.75) 23 Compound Toluene (15) 3.0 100 1 12(0.75) 24 Compound Toluene (15) 3.0 80 1 14 (6.0)

TABLE 4 Number- Weight-average average Yield Activity molecularmolecular Examples (g) (kgmol⁻¹h⁻¹) weight (Mw) weight (Mn) Mw/Mn 20 1.8300 331,000 138,000 2.4 21 2.0 2,700 166,000 77,000 2.2 22 1.7 2,20086,000 21,000 4.1 23 0.37 490 160,000 80,000 2.0 24 1.0 168 160,00057,000 2.8

Examples 25 to 28

The catalysts in Examples 12 and 13 were changed to Compounds 7, 10 and14, and the copolymerization of ethylene and allyl acetate was conductedin a similar manner, or under conditions in which the ethylene pressure,scale or reaction time was changed. The polymerization conditions andresults are shown in Table 5 and Table 6, respectively.

TABLE 5 Allyl Ethylene Catalyst acetate Toluene pressure PolymerizationTime Examples (μmol) (ml) (ml) (MPa) temperature (° C.) (h) 25 Compound7 3 12 3.0 80 12 (10) 26 Compound 7 18.8 56.3 4.0 80 5 (10) 27 Compound10 3 12 3.0 80 12 (10) 28 Compound 14 3 12 3.0 80 14 (10)

TABLE 6 Weight-average Number-average AAC Yield Activity molecularweight molecular weight content Examples (g) (kgmol⁻¹h⁻¹) (Mw) (Mn)Mw/Mn (mol %) 25 0.78 6.5 67,000 29,000 2.3 1.2 26 0.52 10 61,000 29,0002.1 1.2 27 0.35 2.9 24,000 12,000 2.0 1.3 28 0.23 1.6 62,000 22,000 2.83.8

Example 29

In the copolymerization of ethylene and allyl acetate using Compound 6as a catalyst, a scaled up and longtime reaction was performed. That is,Compound 6 (0.029 g, 0.020 mmol), toluene (225 ml) and allyl acetate (75ml) were added into a 500 ml-volume autoclave, ethylene was filled untilthe pressure reached 4.0 MPa, and the solution was stirred at 80° C. for91 hours. After being cooled to room temperature, the reaction solutionwas added to methanol (1.5 l). The precipitated polymer was collected byfiltration and dried under reduced pressure. The yield was 14.9 g andthe catalytic activity was calculated to be 8.2 kgmol⁻¹ h⁻¹. As to themolecular weight of the obtained polymer in terms of polystyrene, theweight average molecular weight (Mw), number average molecular weight(Mn) and Mw/Mn were calculated to be 67,000, 32,000 and 2.1,respectively.

Example 30

Homopolyzation of ethylene was conducted using a reaction solution, inwhich Compound 8 and sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate were reacted in advance,as a catalyst solution. A toluene solution (30 ml) of Compound 8 (5.1mg, 0.010 mmol) and sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate (9.7 mg, 0.011 mmol) wasstirred under argon atmosphere at room temperature for 30 minutes andthe solution was used as a catalyst solution. At that time, it isassumed that an organometallic compound of formula (II) in which R⁴ doesnot exist, i.e.: an organometallic compound represented by the followingformula is generated.

Note that, here, a compound corresponding to Compound 8(R^(1a)=R^(1b)=an isopropyl group, R^(2a)=R^(2b)=a t-butyl group, A¹=anorthophenylene group) is described.

Next, the total amount of the catalyst solution and toluene (45 ml) wereadded into a 120 ml-volume autoclave, and after filling ethylene untilthe pressure reached 3.0 MPa, the solution was stirred at 80° C. for onehour. After being cooled to room temperature, the reaction solution wasadded to methanol (300 ml). The precipitated polymer was collected byfiltration and dried under reduced pressure. The yield was 5.4 g and thecatalytic activity was calculated to be 540 kgmol⁻¹ h⁻¹. As to themolecular weight of the obtained polymer in terms of polystyrene, theweight average molecular weight (Mw), number average molecular weight(Mn) and Mw/Mn were calculated to be 485,000, 211,000 and 2.3,respectively. The amount of the incorporated allyl acetate wascalculated to be 1.4 mol % based on the ¹H-NMR spectrum using1,1,2,2-tetrachloroethane-d2 as a solvent.

Example 31

Copolymerization of ethylene and allyl acetate was performed using acatalyst solution prepared in a similar manner to that described inExample 30. That is, a total amount of the catalyst solution obtained bystirring a toluene solution (30 ml) of Compound 8 (5.1 mg, 0.010 mmol)and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (9.7 mg, 0.011mmol) at room temperature for 30 minutes; toluene (26.3 ml) and allylacetate (18.8 ml) were added into a 120 ml-volume autoclave; and afterethylene was filled until the pressure reached 4.0 MPa, the solution wasstirred at 80° C. for five hours. After being cooled to roomtemperature, the reaction solution was added to methanol (300 ml). Theprecipitated polymer was collected by filtration and dried under reducedpressure. The yield was 0.23 g and the catalytic activity was calculatedto be 4.7 kgmol⁻¹ h⁻¹. As to the molecular weight of the obtainedpolymer in terms of polystyrene, the weight average molecular weight(Mw), number average molecular weight (Mn) and Mw/Mn were calculated tobe 58,000, 28,000 and 2.1, respectively. The amount of the incorporatedallyl acetate was calculated to be 1.1 mol % based on the ¹H-NMRspectrum using 1,1,2,2-tetrachloroethane-d2 as a solvent.

Examples 32 to 37

Homopolymerization of ethylene, copolymerization of ethylene and allylacetate, copolymerization of ethylene and butyl vinyl ether, andcopolymerization of ethylene and methyl acrylate were conducted usingCompound 10; Compound 16; and Compound 17 which was synthesized by asimilar synthesis method to that of Compound 16. The polymerizationconditions and results are shown in Table 7 and Table 8, respectively.

TABLE 7 Ethylene Catalyst Polar olefin Toluene pressure PolymerizationTime Examples (μmol) kind (ml) (ml) (MPa) temperature (° C.) (h) 32Compound 16 None 15 3.0 100 1 (0.75) 33 Compound 17 None 15 3.0 80 1(0.75) 34 Compound 16 Allyl acetate 12 3.0 80 12 (10) (3) 35 Compound 10Butyl vinyl 10 3.0 80 26 (10) ether (5) 36 Compound 16 Butyl vinyl 103.0 80 20 (10) ether (5) 37 Compound 16 Methyl 2.5 3.0 80 15 (10)acrylate (2.5)

TABLE 8 Polar Weight-average Number-average monomer Yield Activitymolecular weight molecular weight content Examples (g) (kgmol⁻¹h⁻¹) (Mw)(Mn) Mw/Mn (mol %) 32 1.6 2,200 110,000 37,000 2.9 — 33 0.53 710 270,000130,000 2.1 — 34 0.18 1.5 20,000 8,900 2.3 0.40 35 0.20 0.76 29,00013,000 2.2 1.0 36 0.070 0.35 22,000 9,300 2.4 0.6 37 0.040 0.24 15,0006,900 2.2 8.6

As discussed above, it was confirmed that the novel metal compound ofthe present invention is very useful as a catalyst for copolymerizationof ethylene and various polar monomers. By using a catalyst compositioncontaining the novel metal compound of the present invention, ahighly-linear polymer can be obtained and it is possible to obtain acopolymer in which a polar monomer is randomly distributed in a polymerchain. Thus, the catalyst composition of the present invention isindustrially very useful because it enables the production of anindustrially-useful functionalized polyolefin.

1. An organometallic compound containing bisphosphine monoxide (BPMO)represented by formula (I) and a metal center M comprising elementsbelonging to Group 10 in the periodic system forming a complex with BPMO

(in the formula, R^(1a), R^(1b), R^(2a) and R^(2b) may be the same ordifferent with each other, and independently represent a substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 14 carbon atoms, asubstituted or unsubstituted biphenyl group or a substituted orunsubstituted aryl group; a pair of R^(1a) and R^(1b) and a pair ofR^(2a) and R^(2b) may be bonded to form a ring structure; and A¹represents an arylene group, a monocyclic heteroarylene group, bivalentheterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon group, or cycloalkenylene group having 3 to 10 carbonatoms).
 2. The organometallic compound as claimed in claim 1,represented by formula (II)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have the samemeanings as in claim 1; and R³ represents a hydrogen atom, alkyl grouphaving 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atomsor bivalent group represented by A² (A² represents arylene group,monocyclic heteroarylene group, monocyclic cycloalkylene group,monocyclic cycloalkenylene group, monocyclic heterocycloalkylene group,monocyclic heterocycloalkenylene group, heterocyclic group or C2-C4alkylene group); R⁴ represents a neutral electron-donating ligand; R³and R⁴ may be crosslinked; when R³ and R⁴ are crosslinked, L representsa single bond or a bivalent group selected from alkylene group,haloalkylene group, alkenylene group and alkynilene group; and when R³and R⁴ are not crosslinked (that is, when L does not exist), R⁴ needsnot to exist; and X⁻ represents a counterion of the cationicoraganometallic compound).
 3. The oraganometallic compound as claimed inclaim 2, wherein ligand R4 is: (i) selected from pyridine, substitutedpyridine, a nitrile compound, ammonia, alkylamine, substitutedalkylamine, arylamine and substituted arylamine; or (ii) represented byformula (1)

(in the formula, W represents C or S; Z is selected from O, S, NH orNR^(a) (R^(a) represents alkyl group or aryl group) and Y needs not toexist; when Y exists, Y is selected from O, S, NH or NR^(b) (R^(b)represents alkyl group or aryl group); R⁵ represents a substituted orunsubstituted alkyl group having 1 to 10 carbon atoms, —OR^(c) (R^(c)represents alkyl group or aryl group) or —NR^(d) ₂ (R^(d) representsalkyl group or aryl group)).
 4. The organometallic compound as claimedin claim 1 represented by formula (III)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), A¹ and X⁻ have thesame meanings as in formula (I) in claim 1 and formula (II) in claim 2;R⁶ represents alkyl group having 1 to 10 carbon atoms, alkyenyl group oraryl group; R⁷, R⁸ and R⁹ independently represent alkyl group or alkoxygroup having 1 to 4 carbon atoms).
 5. The organometallic compound asclaimed in claim 1, represented by formula (IIa)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁶, A¹ and X⁻ havethe same meanings as in claims 1 to 3).
 6. The organometallic compoundas claimed in claim 4, wherein A¹ is substituted or unsubstitutedphenylene group, substituted or unsubstituted naphthylene group orsubstituted or unsubstituted methylene group.
 7. The organometalliccompound as claimed in claim 4, wherein R^(1a), R^(1b), R^(2a) andR^(2b) independently represent branched alkyl group having 3 to 6 carbonatoms.
 8. The organometallic compound as claimed in claim 1, whereinboth of R^(1a) and R^(1b) are isopropyl group or t-butyl group.
 9. Theorganometallic compound as claimed in claim 1, wherein both of R^(2a)and R^(2b) are t-butyl group.
 10. The organometallic compound as claimedin claim 4, wherein X− is selected from SbF₆—, BPh₄-,BArF_(d)—(ArF₄-=[3,5-(CF₃)₂C₆H₃]₄—), BF₄— and PF₆.
 11. Theorganometallic compound as claimed in claim 4, wherein M is palladium.12. The organometallic compound as claimed in claim 1, represented byformula (IV)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, A¹, A², Y, Z, Wand X⁻ have the same meanings as in claims 1 to 3).
 13. Theorganometallic compound as claimed in claim 12, wherein A¹ is asubstituted or unsubstituted phenylene group, a substituted orunsubstituted naphthylene group or a substituted or unsubstitutedmethylene group.
 14. The organometallic compound as claimed in claim 12,represented by formula (V)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), A², R⁵ and X⁻ havethe same meanings as in claims 1 to 3; R¹¹ may not exist or representsalkyl group having 1 to 10 carbon atoms, 1 to 4 of which exist on abenzene ring, and the existing two or more R¹¹'s may be the same ordifferent with each other).
 15. The organometallic compound as claimedin claim 14, wherein A² is substituted or unsubstituted phenylene groupor naphthylene group.
 16. The organometallic compound as claimed inclaim 15, represented by formula (VI)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, R¹¹ and X⁻ havethe same meanings as in claims 1 to 3 and 14).
 17. The organometalliccompound as claimed in claim 12, wherein R^(1a), R^(1b), R^(2a) andR^(2b) are independently branched alkyl group having 3 to 14 carbonatoms.
 18. The organometallic compound as claimed in claim 12, whereinboth of R^(1a) and R^(1b) are isopropyl group.
 19. The organometalliccompound as claimed in claim 12, wherein both of R^(2a) and R^(2b) aret-butyl group.
 20. The organometallic compound as claimed in claim 12,wherein X⁻ is selected from SbF₆ ⁻, BPh₄ ⁻, BArF₄ ⁻, BF₄ ⁻ and PF₆ ⁻.21. The organometallic compound as claimed in claim 12, wherein M ispalladium.
 22. A catalyst composition for polymerizing vinyl monomers,which contains the organometallic compound claimed in claim
 1. 23. Acatalyst composition for copolymerizing non-polar olefins and polarolefins, which contains the organometallic compound claimed in claim 1.24. A method for producing copolymers, comprising a process of reactingnon-polar olefins with polar olefins under polymerization conditions inthe presence of the catalyst composition containing the organometalliccompound claimed in claim
 1. 25. The method for producing copolymers asclaimed in claim 24, wherein polar olefins are represented by formula(VII)CH₂═CR¹³R¹⁴  (VII) (in the formula, R¹³ represents a hydrogen atom ormethyl group; R¹⁴ represents —COOR¹⁵, —CN, —OCOR¹⁵, —OR¹⁵, —CH₂—OCOR¹⁵,—CH₂OH, —CH₂—N(R¹⁶)₂ or —CH₂-Hal (R¹⁵ represents a hydrogen atom, alkylgroup having 1 to 5 carbon atoms or aryl group having 6 to 18 carbonatoms; R¹⁶ represents a hydrogen atom, alkyl group having 1 to 5 carbonatoms, aryl group having 6 to 18 carbon atoms or alkoxycarbonyl group;and Hal represents a halogen atom)).
 26. The method for producingcopolymers as claimed in claim 25, wherein R¹⁴ is —CH₂—OCOR¹⁵, —CH₂OH,—CH₂—N(R¹⁶)₂ or —CH₂-Hal (R¹⁵, R¹⁶ and Hal have the same meanings asdescribed in claim 25).
 27. A method for producing an organometalliccompound represented by formula (III)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁶, R⁷, R⁸, R⁹, A¹and X have the meanings as set forth below), comprising: A process ofreacting free bisphosphine monoxide (BPMO) represented by formula (I)

(in the formula, R^(1a), R^(1b), R^(2a) and R^(2b) may be the same ordifferent with each other, and independently represent a substituted orunsubstituted alkyl group having 1 to 14 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 14 carbon atoms, asubstituted or unsubstituted biphenyl group or a substituted orunsubstituted aryl group; a pair of R^(1a) and R^(1b) and a pair ofR^(2a) and R^(2b) may be bonded to form a ring structure; and A¹represents an arylene group, a monocyclic heteroarylene group,heterocyclic group, alkylene group having 1 to 2 carbon atoms,cycloalkylene group having 3 to 10 carbon atoms, alkenylene group having2 to 8 carbon group, or cycloalkenylene group having 3 to 10 carbonatoms) and (1,5-cyclooctadiene) MR⁶Xa (M represents an element belongingto Group 10 in the periodic system; R⁶ represents alkyl group having 1to 10 carbon atoms, alkenyl group or aryl group; and Xa represents ahalogen atom); and A process of treating the generated(BPMO)(1,5-cyclooctadiene) MR⁶Xa complex with a metal salt representedby M²X (M² represents a monovalent metal ion selected from Ag, Li, Naand K; and X represents a counteranion selected from SbF₆, BPh₄, BArF₄,BF₄ and PF₆) and a compound represented by formula (2)

(in the formula, R⁷, R⁸ and R⁹ independently represent a hydrogen atom,alkyl group having 1 to 4 carbon atoms or alkoxy group).
 28. A methodfor producing an organometallic compound represented by formula (IVa)

(in the formula, M, R^(1a), R^(1b), R^(2a), R^(2b), R⁵, A¹, A² and Xhave the meanings as set forth below), comprising: A process of reactingfree bisphosphine monoxide (BPMO) represented by formula (I)

(in the formula, R^(1a), R^(1b), R^(2a), R^(2b) and A¹ have the meaningsas described in claim 1) with a compound represented by formula (3)

(in the formula, M represents an element belonging to Group 10 in theperiodic system; A² represents an arylene group, a monocyclicheteroarylene group, a monocyclic cycloalkylene group, a monocycliccycloalkenylene group, a monocyclic heterocycloalkylene group, amonocyclic heterocycloalkenylene group, heterocyclic or C2-C4 alkylenegroup; R⁵ represents substituted or unsubstituted alkyl group having 1to 10 carbon atoms, OR^(c) (R^(c) represents alkyl group or aryl group)or NR^(d) ₂ (R^(d) represents alkyl group or aryl group); and Xbrepresents halogen); and a process of adding a metal salt represented byM²X (M² represents a monovalent metal ion selected from Ag, Li, Na andK; and X represents a counteranion selected from SbF₆, BPh₄, BArF₄, BF₄and PF₆) to the reaction product of process (1).